Intermediate for furanyl insecticide

ABSTRACT

The present invention relates to novel (tetrahydro-3-furanyl)methylamino derivatives of the following formula (1): ##STR1## wherein the variables are defined in the specification, which are useful as insecticides.

This application is a divisional of application Ser. No. 08/326,260,filed Oct. 20, 1992, now U.S. Pat. No. 5,434,181.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel (tetrahydro-3-furanyl)methylaminederivatives, insecticides containing the derivatives as an effectiveingredient and intermediates thereof.

2. Description of the Prior Art

Heretofore, a lot of amine compounds having a nitromethylene group, anitroimino group or a cyanoimino group have been known (Japanese PatentLaid-Open Nos. 070468/1989, 171/1990, 157308/1991 and 154741/1992, andothers). In these publications, there is a description that the aminecompounds which contain a heterocyclic group in their molecule show aninsecticidal activity. However, when the present inventors synthesizedthese compounds and examined their insecticidal activity, it was foundthat not all of the amine derivatives having a heterocyclic group showedinsecticidal activity. In other words, compounds showing a noticeableactivity among the compounds described in these publications are limitedto the amine derivatives having a thiazolylmethyl or pyridylmethyl groupas the heterocyclic group, and this fact is described in J. PesticideSci. 18 41 (1993) and others. Further, the compounds which are plannedto commercialize at present are only the derivatives having apyridylmethyl group as the heterocyclic group.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide aminederivatives having a nitro-methylene group, a nitroimino group or acyanoimino group, which are low-toxic and show excellent insecticidalactivity without having the above-mentioned pyridylmethyl group orthiazolylmethyl group as the heterocyclic group.

The present inventors earnestly investigated so as to solve theabove-mentioned problems and, as a result, have found that novel(tetrahydro-3-furanyl)methylamine derivatives of the formula (1) have anexcellent insecticidal activity even in the absence of a pyridylmethylgroup or a thiazolylmethyl group in their molecular structure. On thebasis of the finding, they have completed the present invention.

According to the present invention, there are provided(tetrahydro-3-furanyl)methylamine derivatives represented by a formula(1): ##STR2## where X₁, X₂, X₃, X₄, X₅, X₆ and X₇ represent each ahydrogen atom or an alkyl group having from 1 to 4 carbon atoms; R₁represents a hydrogen atom, an alkyl group having from 1 to 5 carbonatoms, an alkenyl group having 3 carbon atoms, a benzyl group, analkoxyalkyl group having from 2 to 4 carbon atoms (in its whole group),an alkyloxycarbonyl group having from 1 to 3 carbon atoms, a phenoxycarbonyl group, an alkylcarbonyl group having from 1 to 6 carbon atoms,an alkenylcarbonyl group having from 2 to 3 carbon atoms, acycloalkylcarbonyl group having from 3 to 6 carbon atoms, a benzoylgroup, a benzoyl group substituted by alkyl group(s) having from 1 to 4carbon atoms, a benzoyl group substituted by halogen atom(s), a2-furanylcarbonyl group or an N,N-dimethylcarbamoyl group; R₂ representsa hydrogen atom, an amino group, a methyl group, an alkylamino grouphaving from 1 to 5 carbon atoms, a di-substituted alkylamino grouphaving from 2 to 5 carbon atoms (in its whole group), a 1-pyrrolidinylgroup, an alkenylamino group having 3 carbon atoms, an alkynylaminogroup having 3 carbon atoms, a methoxyamino group, an alkoxyalkylaminogroup having from 2 to 4 carbon atoms (in its whole group), a methylthiogroup or --N(Y₁)Y₂ (where Y₁ represents an alkyloxycarbonyl group havingfrom 1 to 3 carbon atoms, a phenoxycarbonyl group, an alkylcarbonylgroup having from 1 to 6 carbon atoms, an alkenylcarbonyl group havingfrom 2 to 3 carbon atoms, a cycloalkylcarbonyl group having from 3 to 6carbon atoms, a benzoyl group, a benzoyl group substituted by alkylgroup(s) having from 1 to 4 carbon atoms, a benzoyl group substituted byhalogen atom(s), a 2-furanylcarbonyl group, an N,N-dimethylcarbamoylgroup, a (tetrahydro-3-furanyl)methYl group or a benzyl group, and Y₂represents a hydrogen atom or an alkyl group having from 1 to 5 carbonatoms); and Z represents ═N--NO₂, ═CH--NO₂ or ═N--CN; insecticidescontaining the derivatives as an effective ingredient; and intermediatesfor producing the compounds of the formula (1) represented by a formula(2): ##STR3## where X₁, X₂, X₃, X₄, X₅, X₆ and X₇ represent each ahydrogen atom or an alkyl group having from 1 to 4 carbon atoms; R₁₀represents an alkyl group having from 1 to 5 carbon atoms or a benzylgroup; and Rll represents an alkyl group having from 1 to 5 carbon atomsor a benzyl group.

The novel (tetrahydro-3-furanyl)methylamine derivatives of the formula(1) according to the invention are excellent compounds having a highinsecticidal power and broad insecticidal spectrum. Further,agricultural chemicals containing the novel(tetrahydro-3-furanyl)methylamine derivatives of the formula (1)according to the invention have outstanding characteristics asinsecticides and hence are useful.

DETAILED DESCRIPTION OF THE INVENTION

Specific examples of the alkyl group for X₁, X₂, X₃, X₄, X₅, X₆, and X₇in the above formulae (1) and (2) include a methyl group, an ethylgroup, an n-propyl group, an iso-propyl group, a tert-butyl group, andthe like, preferably a methyl group.

Specific examples of the alkyl group for R₁ include a methyl group, anethyl group, an n-propyl group, an iso-propyl group, an n-butyl group,an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-pentylgroup, and the like.

Specific examples of the alkenyl group for R₁ include a 1-propenylgroup, a 2-propenyl group, and the like.

Specific examples of the alkoxyalkyl group for R₁ include amethoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, aniso-propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, andthe like.

Specific examples of the alkyloxycarbonyl group for R₁ include amethyloxycarbonyl group, an ethyloxycarbonyl group, ann-propyloxycarbonyl group, an iso-propyloxycarbonyl group, and the like.

Specific examples of the alkylcarbonyl group for R₁ include amethylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group,an iso-propylcarbonyl group, an n-butylcarbonyl group, aniso-butylcarbonyl group, a sec-butylcarbonyl group, a tert-butylcarbonylgroup, an n-pentylcarbonyl group, an n-hexylcarbonyl group, and thelike.

Specific examples of the alkenylcarbonyl group for R₁ include avinylcarbonyl group, a 1-methylvinylcarbonyl group, and the like.

Specific examples of the cycloalkylcarbonyl group for R₁ include acyclopropylcarbonyl group, a cyclobutylcarbonyl group, acyclopentylcarbonyl group, a cyclohexylcarbonyl group, and the like.

Specific examples of the benzoyl group substituted by alkyl group(s) forR₁ include a 2-methylbenzoyl group, a 3-methylbenzoyl group, a4-methylbenzoyl group, a 4-tert-butylbenzoyl group, and the like.

Specific examples of the benzoyl group substituted by halogen atom(s)for R₁ include a 2-chlorobenzoyl group, a 3-chlorobenzoyl group, a4-chlorobenzoyl group, a 3,4-dichloro-benzoyl group, a 4-fluorobenzoylgroup, and the like.

Although R₁ can take various substituents as described above, it ispreferably a hydrogen atom, an alkylcarbonyl group having from 1 to 4carbon atoms or a cyclopropylcarbonyl group.

Specific examples of the alkylamino group for R₂ include a methylaminogroup, an ethylamino group, an n-propyl-amino group, an iso-propylaminogroup, an n-butylamino group, an iso-butylamino group, a sec-butylaminogroup, a tert-butylamino group, an n-pentylamino group, and the like,preferably a methylamino group.

Specific examples of the di-substituted alkylamino group for R₂ includea dimethylamino group, a diethylamino group, an N-methyl-N-ethylaminogroup, an N-methyl-N-n-propylamino group, an N-methyl-N-n-butylaminogroup, and the like, preferably a dimethylamino group.

Specific examples of the alkenylamino group for R₂ include a1-propenylamino group, a 2-propenylamino group, and the like.

Specific examples of the alkynylamino group for R₂ include apropargylamino group, and the like.

Specific examples of the alkoxyalkylamino group for R₂ include amethoxymethylamino group, an ethoxymethylamino group, ann-propoxymethylamino group, an iso-propoxymethylamino group, amethoxyethylamino group, an ethoxyethylamino group, and the like.

Specific examples of the alkyloxycarbonyl group denoted by Y₁ for R₂include a methyloxycarbonyl group, an ethyloxy-carbonyl group, ann-propyloxycarbonyl group, an iso-propyloxy-carbonyl group, and thelike.

Specific examples of the alkylcarbonyl group denoted by Y₁ for R₂include a methylcarbonyl group, an ethylcarbonyl group, ann-propylcarbonyl group, an iso-propylcarbonyl group, an n-butylcarbonylgroup, an iso-butylcarbonyl group, a sec-butyl-carbonyl group, atert-butylcarbonyl group, an n-pentylcarbonyl group, an n-hexylcarbonylgroup, and the like, preferably a methylcarbonyl group, an ethylcarbonylgroup, an n-propylcarbonyl group, an iso-propylcarbonyl group, ann-butylcarbonyl group, an iso-butylcarbonyl group, a sec-butylcarbonylgroup and a tert-butylcarbonyl group.

Specific examples of the alkenylcarbonyl group denoted by Y₁ for R₂include a vinylcarbonyl group, a 1-methyl-vinylcarbonyl group, and thelike.

Specific examples of the cycloalkylcarbonyl group denoted by Y₁ for R₂include a cyclopropylcarbonyl group, a cyclobutylcarbonyl group, acyclopentylcarbonyl group, a cyclo-hexylcarbonyl group, and the like,preperably a cyclopropyl-carbonyl group.

Specific examples of the benzoyl group substituted byalkyl group(s)denoted by Y₁ for R₂ include a 2-methylbenzoyl group, a 3-methylbenzoylgroup, a 4-methylbenzoyl group, a 4-tert-butylbenzoyl group, and thelike.

Specific examples of the benzoyl group substituted by halogen atom(s)denoted by Y₁ for R₂ include a 2-chlorobenzoyl group, a 3-chlorobenzoylgroup, a 4-chlorobenzoyl group, a 3,4-dichlorobenzoyl group, a 4-fluorobenzoyl group, and the like.

Specific examples of the alkyl group denoted by Y₂ for R₂ include amethyl group, an ethyl group, an n-propyl group, an iso-propyl group, ann-butyl group, an iso-butyl group, a sec-butyl group, a tert-butylgroup, an n-pentyl group, and the like, preferably a methyl group.

In the formula (1), compounds in which R₁ and Y₁ are concurrently analkylcarbonyl group having from 1 to 4 carbon atoms or acyclopropylcarbonyl group are preferred from the viewpoint of bothinsecticidal activity and production method.

Compounds of the formula (1) may be produced in accordance with any ofthe following methods (A) through (F) depending of the substituentsinvolved.

Method (A):

The production of compounds of an formula (1A) where R₁ stands for R₃and R₂ for NR₅ R₆ in the formula (1) is shown by a reaction scheme (I):##STR4## where X₁, X₂, X₃, X₄, X₅, X₆ and X₇ have the same meanings asmentioned above; R₃ represents a hydrogen atom, an alkyl group havingfrom 1 to 5 carbon atoms, an alkenyl group having 3 carbon atoms, abenzyl group or an alkoxyalkyl group having from 2 to 4 carbon atoms; R₄represents an alkylthio group having from 1 to 5 carbon atoms or abenzylthio group; R₅ represents an alkyl group having from 1 to 5 carbonatoms, an alkenyl group having 3 carbon atoms, an alkynyl group having 3carbon atoms, a methoxy group, an alkoxyalkyl group having from 2 to 4carbon atoms, a (tetrahydro-3-furanyl)methyl group or a benzyl group; R₆represents a hydrogen atom or an alkyl group having from 1 to 5 carbonatoms, or R₅ and R₆ are bonded together to form a 1-pyrrolidinyl group;and Z has the same meaning as mentioned above.

Namely, the compounds of the formula (1A) may be produced with ease byreacting a compound of the formula (3) and an amine of the formula (4)in various solvents in the presence of a base or a catalyst as occasiondemands.

As the base, it is possible to use an excessive amount of the amine, ora carbonate such as potassium carbonate and sodium carbonate, aphosphate such as tripotassium phosphate, trisodium phosphate,dipotassium hydrogenphosphate and disodium hydrogenphosphate, an acetatesuch as sodium acetate and potassium acetate, or the like.

As the catalyst, it is possible to use an organic base such as4-(dimethylamino)pyridine, DBU, triethylamine and diazabicycloundecene,ion exchange resin, silica gel, zeolite, or the like.

The solvent to be used may include not only water but also alcohols suchas methanol, ethanol, propanol and butanol, aromatic hydrocarbons suchas benzene, toluene and xylene, aliphatic hydrocarbons such as hexane,heptane and petroleum benzine, aprotic polar solvents such asdimethylformamide, dimethylacetamide, dimethylsulfoxide,1,3-dimethyl-2-imidazolidinone and 1-methyl-2-pyrrolidinone, ethers suchas ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuranand dioxane, nitriles such as acetonitrile and propionitrile, ketonessuch as acetone and diisopropyl ketone, and the like.

The reaction temperature and the reaction time can be varied over wideranges. In general, the reaction temperature is in the range of from-20° to 200° C., preferably from 0° to 150° C.; and the reaction time isin the range of from 0.01 to 50 hours, preferably from 0.1 to 15 hours.

The compounds of the formula (3) in the reaction scheme (I) can beproduced in accordance with, for example, a procedure described inJapanese Patent Laid-Open No. 70468/1989. The compounds of the formulae(4) in the reaction scheme (I) can be produced by methods known in theart.

Method B:

The production of compounds of an formula (1B) where R₁ stands for R₇and R₂ for R₈ in the formula (1) is shown by a reaction scheme (II):##STR5## where X₁, X₂, X₃, X₄, X₅, X₆ and X₇ have the same meanings asmentioned above; R₇ is a hydrogen atom, an alkyl group having from 1 to5 carbon atoms, an alkenyl group having 3 arbon atoms, a benzyl group oran alkoxyalkyl group having from 2 to 4 carbon atoms; R₈ represents ahydrogen atom, an amino group, an alkyl group having from 1 to 3 carbonatoms, an alkylamino group having from 1 to 5 carbon atoms, adi-substituted alkylamino group having from 2 to 5 carbon atoms, a1-pyrrolidinyl group, an alkenylamino group having 3 carbon atoms, analkynylamino group having 3 carbon atoms, a methoxyamino group, analkoxyalkylamino group having from 2 to 4 carbon atoms, an alkylthiogroup having from 1 to 5 carbon atoms or a benzylthio group; R₉represents an amino group, an alkoxy group having from 1 to 5 carbonatoms, an alkylthio group having from 1 to 5 carbon atoms or anbenzylthio group; and Z has the same meaning as described above.

Namely, the compounds of the formula (1B) may be produced with ease andin high yield by reacting a compound of the formula (5) and a compoundof the formula (6).

The reaction is effected with ease in various solvents in the presenceof a base or a catalyst as occasion demands.

As the base, it is possible to use a carbonate such as potassiumcarbonate and sodium carbonate, a phosphate such as tripotassiumphosphate, trisodium phosphate, dipotassium hydrogenphosphate anddisodium hydrogenphosphate, an acetate such as sodium acetate andpotassium acetate, or the like.

As the catalyst, it is possible to use an organic base such as4-(dimethylamino)pyridine, DBU, triethylamine and diazabicycloundecene,a sulfonic acid such as p-toluenesulfonic acid and methanesulfonic acid,a mineral acid such as sulfuric acid, hydrogen chloride and phosphoricacid, ion exchange resin, silica gel, zeolote, or the like.

The solvent to be used may include not only water but also alcohols suchas methanol, ethanol, propanol and butanol, aromatic hydrocarbons suchas benzene, toluene and xylene, aliphatic hydrocarbons such as hexane,heptane and petroleum benzine, aprotic polar solvents such asdimethylformamide, dimethylacetamide, dimethylsulfoxide,1,3-dimethyl-2-imidazolidinone and 1-methyl-2-pyrrolidinone, ethers suchas ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuranand dioxane, nitriles such as acetonitrile and propionitrile, ketonessuch as acetone and diisopropyl ketone, and the like.

The reaction temperature and the reaction time can be varied over wideranges. In general, the reaction temperature is in the range of from-20° to 200° C., preferably from 0° to 150° C.; and the reaction time isin the range of from 0.01 to 50 hours, preferably from 0.1 to 15 hours.

The compounds of a formula (5) in the reaction scheme (II) may beproduced in accordance with procedures of a reaction scheme (IIA):##STR6## where X₁, X₂, X₃, X₄, X₅, X₆ and X₇ have the same meanings asdescribed above; W₃ represents a halogen atom, a toluenesulfonyloxygroup, a methanesulfonyloxy group or a trifluoromethanesulfonyloxygroup; and M represents a sodium atom or a potassium atom; R₇ representsa hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, analkenyl group having 3 carbon atoms, a benzyl group or an alkoxyalkylgroup having from 2 to 4 carbon atoms.

Namely, the compounds of the formula (5) can be produced by halogenating(tetrahydro-3-furanyl)methanol derivatives with a halogenating agentsuch as thionyl chloride, phosphorus oxychloride, phosphorus tribromide,triphenyl-phosphine/carbon tetrabromide and triphenylphosphine/carbontetrachloride, or sulfonating the derivatives with a sulfonating agentsuch as tosyl chloride, methanesulfonyl chloride andtrifluoromethane-sulfonic acid anhydride, followed by reaction accordingto known amine synthesis methods such as the Gabriel Synthesis usingpotassium phthalimide and the Delepine Reaction usinghexamethylenetetramine or by reacting with an alkylamine.

The compounds of the formula (6) in the reaction scheme (II) can beproduced by a procedure described in Chem. Ber., vol. 100, p591, andothers.

Method (C):

The production of compounds of a formula (1C) where R₁ stands for R₇, R₂for SW₁ and Z for ═N--NO₂ in the formula (1) is shown by a reactionscheme (III). ##STR7## where X₁, X₂, X₃, X₄, X₅, X₆ and X₇ have the samemeaning as described above; R₇ represents a hydrogen atom, an alkylgroup having from 1 to 5 carbon atoms, a benzyl group or an alkoxyalkylgroup having from 2 to 4 carbon atoms; W₁ represents an alkyl grouphaving from 1 to 4 carbon atoms; and W₂ represents an imide group.

Namely, the compounds of the formula (1C) can be produced with ease andin high yield by reacting a compound of the formula (5) with a compoundof the formula (7).

The reaction is effected with ease in various solvents in the presenceof a base as occasion demands.

The base to be used includes alkali metal hydroxides such as sodiumhydroxide and potassium hydroxide, alkaline earth metal hydroxide suchas magnesium hydroxide and calcium hydroxide, alkali metal hydrides suchas sodium hydride and potassium hydride, alkali metal alcoholares suchas sodium methylate and sodium ethylate, alkali metal oxides such assodium oxide, carbonates such as potassium carbonate and sodiumcarbonate, phosphates such as tripotassium phosphate, trisodiumphosphate, dipotassium hydrogenphosphate and disodiumhydrogenphosphate,. acetates such as sodium acetate and potassiumacetate, organic bases such as pyridine, 4-(dimethylamino)pyridine, DBU,triethylamine and diazabicycloundecene, and the like.

The solvents to be used may include not only water but also alcoholssuch as methanol, ethanol, propanol and butanol, aromatic hydrocarbonssuch as benzene, toluene and xylene, aliphatic hydrocarbons such ashexane, heptane and petroleum benzine, aprotic polar solvents such asdimethylformamide, dimethylacetamide, dimethylsulfoxide,1,3-dimethyl-2-imidazolidinone and 1-methyl-2-pyrrolidinone, ethers suchas ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuranand dioxane, nitriles such as acetonitrile and propionitrile, ketonessuch as acetone and diisopropyl ketone, and the like.

The reaction temperature and the reaction time can be varied over wideranges. In general, the reaction temperature is in the range from -30°to 200° C., preferably from -20° to 150° C.; and the reaction time is inthe range of 0.01 to 50 hours, preferably from 0.1 to 15 hours.

The compound of the formula (5) in the reaction scheme (III) can beproduced by the procedure of the above-described reaction scheme (IIA).

The compound of the formula (7) in the reaction scheme (III) can beproduced in accordance with procedures of Japanese Patent Laid-Open No.9173/1993 and others.

Method (D):

The production of compounds of a formula (1D) where R₁ stands for Y₁, R₂for NY₁ Y₃, and Z for Z₁ in the formula (1) is shown by a reactionscheme (IV): ##STR8## where X₁, X₂, X₃, X₄, X₅, X₆ and X₇ have the samemeaning as described above; Y₃ represents a hydrogen atom or an alkylgroup having from 1 to 5 carbon atoms; Y₁ represents an alkyloxycarbonylgroup having from 1 to 3 carbon atoms, a phenoxycarbonyl group, analkylcarbonyl group having from 1 to 6 carbon atoms, an alkenylcarbonylgroup having from 2 to 3 carbon atoms, a cycloalkylcarbonyl group havingfrom 3 to 6 carbon atoms, a benzoyl group, a benzoyl group substitutedby alkyl group(s) having from 1 to 4 atoms, a benzoyl group substitutedby halogen atom(s), a 2-furanyl-carbonyl group, or anN,N-dimethylcarbamoyl group; and Z₁ represents ═N--NO₂ or ═N--CN.

The compounds of the formula (1D) may be produced with ease and in highyield by reacting. a compound of the formula (8) with a compound of theformula (9).

The reaction is effected with ease in various solvents in the presenceof a base.

The base to be used includes alkali metal hydroxides such as sodiumhydroxide and potassium hydroxide, alkaline earth metal hydroxides suchas magnesium hydroxide and calcium hydroxide, alkali metal hydrides suchas sodium hydride and potassium hydride, alkali metal alcoholates suchas sodium methylate and sodium ethylate, alkali metal oxides such assodium oxide, carbonates such as potassium carbonate and sodiumcarbonate, phosphates such as tripotassium phosphate, trisodiumphosphate, dipotassium hydrogenphosphate and disodium hydrogenphosphate,acetates such as sodium acetate and potassium actate, organic bases suchas pyridine, 4-(dimethylamino)pyridine, DBU, triethylamine anddiazabicycloundecene, and the like.

The solvents to be used may include not only water but also alcoholssuch as methanol, ethanol, propanol and butanol, aromatic hydrocarbonssuch as benzene, toluene and xylene, aliphatic hydrocarbons such ashexane, heptane and petroleum benzine, aprotic polar solvents such asdimethylformamide, dimethylacetamide, dimethylsulfoxide,1,3-dimethyl-2-imidazolidinone and 1-methyl-2-pyrrolidinone, ethers suchas ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuranand dioxane, nitriles such as acetonitrile and propionitrile, ketonessuch as acetone and diisopropyl ketone, chlorinated solvents such asmethylene chloride and chloroform, and the like.

The reaction temperature and the reaction time can be varied over wideranges. In general, the reaction temperature is in the range of from-20° to 200° C., preferably from 0°-150° C.; and the reaction time is inthe range of from 0.01 to 50 hours, preferably from 0.1 to 15 hours.

The compound of the formula (8) in the reaction scheme (IV) can beproduced in accordance with the procedure of the reaction scheme (I) or(II).

The compound of the formula (9) in the reaction scheme (IV) can beproduced from known carboxylic acids in accordance with known methodsfor the synthesis of acid chlorides.

Method (E):

The production of compounds of a formula (1E) where R₁ stands for Y₁, R₂for NY₄ Y₅, and Z for Z₁ is shown by a reaction scheme (V): ##STR9##where X₁, X₂, X₃, X₄, X₅, X₆ and X₇ have the same meanings as describedabove; Y₄ represents an alkyl group having from 1 to 5 carbon atoms; Y₅represents an alkyl group having from 1 to 5 carbon atoms; Y₁ representsan alkyloxycarbonyl group having from 1 to 3 carbon atoms, aphenoxycarbonyl group, an alkylcarbonyl group having from 1 to 6 carbonatoms, an alkenylcarbonyl group having from 2 to 3 carbon atoms, acycloalkylcarbonyl group having from 3 to 6 carbon atoms, a benzoylgroup, a benzoyl group substituted by alkyl group(s) having from 1 to 4carbon atoms, an benzoyl group substituted by halogen atom(s), a2-furanylcarbonyl group or an N,N-dimethylcarbamoyl group; and Z₁represents ═N--NO₂ or ═N--CN.

The compounds of the formula (1E) can be produced with ease and in highyield by reacting a compound of the formula (10) with a compound of theformula (9).

The reaction is effected with ease in various solvents in the presenceof a base.

The base to be used includes alkali metal hydroxides such as sodiumhydroxide and potassium hydroxide, alkaline earth metal hydroxides suchas magnesium hydroxide and calcium hydroxide, alkali metal hydrides suchas sodium hydride and potassium hydride, alkali metal alcoholates suchas sodium methylate and sodium ethylate, alkali metal oxides such assodium oxide, carbonates such as potassium carbonate and sodiumcarbonate, phosphates such as tripotassium phosphate, trisodiumphosphate, dipotassium hydrogenphosphate and disodium hydrogenphosphate,acetates such as sodium acetate and potassium acetate, organic basessuch as pyridine, 4-(dimethylamino)pyridine, DBU, triethylamine anddiazabicycloundecene, and the like.

The solvents to be used may include not only water but also alcoholssuch as methanol, ethanol, propanol and butanol, aromatic hydrocarbonssuch as benzene, toluene and xylene, aliphatic hydrocarbons such ashexane, heptane and petroleum benzine, aprotic polar solvents such asdimethylformamide, dimethylacetamide, dimethylsulfoxide,1,3-dimethyl-2-imidazolidinone and 1-methyl-2-pyrrolidinone, ethers suchas ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuranand dioxane, nitriles such as acetonitrile and propionitrile, ketonessuch as acetone and diisopropyl ketone, chlorinated solvents such asmethylene chloride and chloroform, and the like.

The reaction temperature and the reaction time can be varied over wideranges. In general, the reacation temperature is in the range of from-20° to 200° C., preferably from 0° to 150° C., and the reaction time isin the range of from 0.01 to 50 hours, preferably from 0.1 to 15 hours.

The compound of the formula (10) in the reaction scheme (V) can beproduced in accordance with the procedure of the reaction scheme (I) or(II).

The compound of the formula (9) in the reaction scheme (V) can beproduced from known carboxylic acids in accordance with known methodsfor the production of acid chlorides.

Method (F):

The production of compounds of a formula (1F) where R₁ stands for ahydrogen atom, R₂ for NHR₁₁, and Z for ═N--NO₂ is shown by a reactionscheme (VI). ##STR10## where X₁, X₂, X₃, X₄, X₅, X₆ and X₇ have the samemeanings as described above; R₁₀ represents an alkyl group having from 1to 5 carbon atoms or a benzyl group; and R₁₁ represents an alkyl grouphaving from 1 to 5 carbon atoms or a benzyl group.

Namely, the compounds of the formula (1F) can be produced with ease andin high yield by treating a compound of the formula (2) under acidicconditions.

The reaction is effected with ease in various solvents in the presenceof an acid or, if necessary, a catalyst.

The acid or catalyst to be used may include sulfonic acids such asp-toluenesulfonic acid and methanesulfonic acid, mineral acids such assulfuric acid, hydrochloric acid and phosphoric acid, ion exchangeresin, silica gel, zeolite, and the like. The solvents to be used mayinclude not only water but also alcohols such as methanol, ethanol,propanol and butanol, aromatic hydrocarbons such as benzene, toluene andxylene, aliphatic hydrocarbons such as hexane, heptane and petroleumbenzine, aprotic polar solvents such as dimethylformamide,dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone and1-methyl-2-pyrrolidinone, ethers such as ethyl ether, diisopropyl ether,1,2-dimethoxyethane, tetrahydrofuran and dioxane, nitriles such asacetonitrile and propionitrile, ketones such as acetone and diisopropylketone, and the like.

The reaction temperature and the reaction time can be varied over wideranges. In general, the reaction temperature is in the range of from-20° to 150° C., preferably from room temperature to 100° C.; and thereaction time is in the range of from 0.01 to 50 hours, preferably from0.1 to 10 hours.

The compound of the formula (2) in the reaction scheme (VI) can beproduced by the procedure of a reaction scheme (VIA): ##STR11## whereX₁, X₂, X₃, X₄, X₅, X₆ and X₇ have the same meanings as described above;W₃ represents a chlorine atom, a bromine atom, a toluenesulfonyloxygroup, a methanesulfonyloxy group or a trifluoromethanesulfonyloxygroup; R₁₀ represents an alkyl group having from 1 to 5 carbon atoms ora benzyl group; and R₁₁ represents an alkyl group having from 1 to 5carbon atoms or a benzyl group.

The compounds of the formula (2) can be produced with ease and in highyield by reacting a compound of the formula (11) with a compound of theformula (12).

The reaction is effected with ease in various solvents in the presenceof a base or catalyst as occasion demands.

The base to be used includes alkali metal hydroxides such as sodiumhydroxide and potassium hydroxide, alkaline earth metal hydroxide suchas magnesium hydroxide and calcium hydroxide, alkali metal hydrides suchas sodium hydride and potassium hydride, alkali metal alcoholates suchas sodium methylate and sodium ethylate, alkali metal oxides such assodium oxide, carbonates such as potassium carbonate and sodiumcarbonate, phosphates such as tripotassium phosphate, trisodiumphosphate, dipotassium hydrogenphosphate and disodium hydrogenphosphate,acetates such as sodium acetate and potassium acetate, organic basessuch as 4-(dimethylamino)pyridine, DBU, triethylamine anddiazabicycloundecene, and the like.

The solvents to be used may include not only water but also alcoholssuch as methanol, ethanol, propanol and butanol, aromatic hydrocarbonssuch as benzene, toluene and xylene, aliphatic hydrocarbons such ashexane, heptane and petroleum benzine, aprotic polar solvents such asdimethylformamide, dimethylacetamide, dimethylsulfoxide,1,3-dimethyl-2-imidazolidinone and 1-methyl-2-pyrrolidinone, ethers suchas ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuranand dioxane, nitriles such as acetonitrile and propionitrile, ketonessuch as acetone and diisopropyl ketone, and the like.

The reaction temperature and the reaction time can be varied over wideranges. In general, the reaction temperature is in the range of from-30° to 200° C., preferably from -20° to 150° C.; and the reaction timeis in the range of from 0.01 to 50 hours, preferably from 0.1 to 15hours.

The compound of the formula (11) in the reaction scheme (VIA) can beproduced by-halogenating (tetrahydro-3-furanyl)methanol derivatives witha halogenating agent such as thionyl chloride, phosphorus oxychloride,phosphorus tribromide, triphenylphosphine/carbon tetrabromide andtriphenylphosphine/carbon tetrachloride, or sulfonating the derivativeswith a sulfonating agent such as tosyl chloride, methanesulfonylchloride and trifluoromethanesulfonic acid anhydride.

The compound of the formula (12) in the reaction scheme (VIA) can beproduced from a monoalkyl-substituted nitroguanidine ormonobenzyl-substituted nitroguanidine, a primary amine and formaldehyde.

The compounds of the formula (1) may exist as isomers (cis- andtrans-isomers) and tautomers. Further, since an asymmetric carbon atomis present at the 3rd position of the tetrahydrofuran ring, thecompounds may exist as optically active isomers, racemic modifications,and mixtures thereof in optional proportions. Where the tetrahydrofuranring has alkyl substituents, diastereomers may exist in some cases.These isomers can exist as mixtures in optional proportions. All ofthese isomers, tautomers and mixtures thereof are also included in thescope of the present invention.

The amine derivatives having a nitromethylene group, a nitroimino groupor a cyanoimino group represented by the formula (1) according to thepresent invention are characterized by having a(tetrahydro-3furanyl)methyl group. For example, when the oxygen atom inthe tetrahydrofuran ring is replaced by a sulfur atom or a nitrogenatom, the insecticidal activity of the derivatives is completely lost.It is also characteristics of the derivatives that the oxygen atom ispresent at the 3rd position. Tetrahydro-2-furylmethylamine derivatives,which has an oxygen atom at the 2nd position, show entirely noinsecticidal activity. In other words, only(tetrahydro-3-furanyl)methylamine derivatives, which are saturatedheterocyclic derivatives of a very limited structure, exhibitinsecticidal activity very characteristically.

The derivatives of the formula (1) according to the invention have apowerful insecticidal activity and can be used as an insecticide in avariety of fields such as an agriculture, horticulture, livestockindustry, forestry, forestry, disinfection and houses. The derivative ofthe formula (1) of the invention show exactly a high control effect onharmful insects without involving any phyto-toxicity to cultivatedplants, higher animals and an environment.

Insect pest to which the derivatives of the formula (1) according to theinvention can be applied, for instance, include:

LEPIDOPTERA

Pseudaletia separata Walker--rice armyworm

Sesamia inferens Walker--pink borer

Narangata aenescens Moore--green rice caterpillar

Agrotis ipsilon Hufnagel--black cutworn

Anomis flava Fabricius--cotton leaf caterpillar

Helicoverpa armigera Hubner--corn earworm

Spodoptera exigua Hubnet--beet armyworn

Spodoptera litura Fabricius--Common cutworn

Agrotis segetum Denis et Schiffermuller--cutworn

Mamestra brassicae Linnaeus--cabbage armyworn

Autographa nigrisigna Walker--beet semi-looper

Chilo suppressalis Walker--rice stem borer

Cnaphalocrocis medinalis Guenee--rice leafroller

Scirpophaga incertulas Walker--yellow rice borer

Ectomyelois pyrivorella Matsumura--pear fruit moth

Hellulla undalis Fabricius--cabbage webworn

Maruca testulalis Hubner--bean pod borer

Parnara guttata Bremer et Grey--rice skipper

Pectinophora gossypiella Saunders--pink bollworn

Phthorimaea operculella Zeller--potato tuberworn

Pieris rapae crucivota Boisduval--common cabbage worm

Plodia interpunctella Hubher--Indian meal worm

Adoxophyes sp.

Phyllonorycter ringoniella Matsumura--apple leafminer

Phyllocnistis citrella Stainton--citrus leafminer

Eupoecillia ambiguella Hubner--grape cochylid

Graholita molesta Busck--oriental fruit moth

Leguminivora glycinivorella Matsumara--soybean pod borer

Carposina niponensis Walsingham--peach fruit moth

Paranthrene regalis Butler--grape clearwing moth

Caloptilia theivora Walsingham--tea leafroller

Plutella xylostella Linnaeus--diamondback moth

Tinea translucens Meyrick--casemaking clothes moth

HEMIPTERA

Bemisia tabaci Gennadius--sweetpotato whitefly

Trialeurodes vaporariorum Westwood--greenhouse whitefly

Aleurocanthus spiniferus Quaintance--citrus spiny whitefly

Aphis gossypii Glover--cotton aphid

Aphis citricola van der Goot--spiraea aphid

Eriosoma lanigerum Hausmann--woolly apple aphid

Myzus persicae Sulzer--green peach aphid

Brevicorvne brassicae Linnaeus--cabbage aphid

Lipaphis erysimi Kaltenbach--turnip aphid

Aphis craccivora Koch--cowpea aphid

Toxoptera aurantii Boyer de Fonscolombe--black citrus aphid

Toxoptera citricidus Kirkaldy--tropical citrus aphid

Viteus vitifolii Fitch--grapeeleaf louse

Schizaphis graminum Rondani--greenbug

Aulacorthum solani Kaltenbach--foxglove aphid

Empoasca onukii Matsuda--tea green leaf hopper

Arboridia apicalis Nawa--grape leafhopper

Laodelphax striatellus Fallen--small brown planthopper

Nilaparvata lugens Stal--brown rice hopper

Sogatella furcifera Horvath--whitebacked rice planthopper

Nephotettix cincticeps Uhler--green rice leafhopper

Nephotettix virescens Distant--green rice leafhopper

Cofana spectra Distanrt--rice leafhopper

Ceroplastes rubens Maskell--red wax scale

Saissetia oleae Bernard--black scale

Comstockaspis perniciosa Comstock--San Jose scale

Lepidosaphes ulmi Linnaeus--oystershell scale

Aonidiella aurantii Maskell--California red scale

Chrysomphalus ficus Ashmead--Florida red scale

Unaspis vanonensis Kuwana--arrowhead scale

Pseudococcus comstocki Kuwana--Comstock mealybug

Planococcus citri Risso--citrus mealybug

Icerya purchasi Maskell--cottonycushion scale

Pyslla mali Schmidberger--apple sucker

Diaphorina citri Kuwayama--citrus psylla

Nezara viridula Linnaeus--southern green stink bug

Riptortus clavatus Thunberg--bean bug

Stephanitis nashi Esaki et Takeya--pear lace bug

COLEOPTERA

Lissorhoptrus oryzophilus Kuschhel--rice water weevil

Oulema oryzae Kuwayama--rice leaf beetle

Phyllotreta striolata Fabricius--striped flea beetle

Leptinotarsa decemlineata Say--Colorado potato beetle

Chaetocnema concinna Marshall

Diabrotica spp

Sitophilus zeamais Motschulsky--maize weevil

Carpophilus hemipterus Linnaeus--driedfruit beetle

Epilachna vigintioctopunctata Fabricius--twenty-eight-spotted ladybird

Acanthoscelides obtectus Say--bean weevil

Callosobruchus chinensis Linnaeus--adzuki bean weevil

Callosobruchus maculatus Fabricius--cowpea weevil

Anomala cuprea Hope--cupreous chafer

Anomala rufocuprea Motschulsky--soybean beetle

Popilla japonica Newman--japanese beetle

Anoplophora malasiaca Thomson--whitespotted longicom beetle

Lasioderma serricorne Fabicius--cigarette beetle

Anthrenus verbasci Linnaeus--varied carpet beetle

Tribolium castaneum Herbst--red flour beetle

Lyctus brunneus Stephens--powderpost beetle

HYMENOPTERA

Culex piplens pallens Coquilett

Culex piplens molestus

Anopheles sinensis

Aedes albopictus

Agromyza oryzae Munakata--rice leafminer

Asphondylia sp.--soybean pod gall midge

Chlorops oryzae Matsumura--rice stem maggot

Hydrellia griseola Fallen--rice leafminer

Musca domestica vicina Macquart--house fly

Phormia regina Meigen

Delia antiqua Meigen--onion maggot

Dacus (Zeugodacus) cucurbitae Coquillett--melon fly

Dacus (Bactrocera) dorsalis Hendel--oriental fruit fly

THYSANOPTERA

Thrips tabaci Lindeman--onion thrips

Ponticulothrips diospyrosi Haga et Okajima

Thrips palmi Karny

Stenchaetothrips biformis Bagnall--rice thrips

Scirtothrips dorsalis Hood--yellow tea thrips

ORTHOPTERA

Periplaneta fuliginosa Setville

Periplaneta japonica Karny

Periplaneta americana Linn--American cockroach

Blattella germanica Linne

Oxya yezoensis Shiraki--rice grasshopper

Locusta migratoria Linnaeus--Asiatic locust

HYMENOPTERA

Athalia rosae ruficornis Jakovlev--cabbage sawfly

ACARINA

Tetranychus urticae Koch--two-spotted spider mite

Tetranychus kanzawai Kishida--Kanzawa spider mite

Panonychus ulmi Koch--European red mite

Polyphagotarsonemus latus Branks--broad mite

Aculops pelekassi Keifer--pink citrus rust mite

Eriophyes chibaensis Kadono

Ornithonyssus bacoti Hirst

TROMBICULIDAE

Tyrophagus putrescentiae Schrank--dog flea

Pediculus humanus humanus De Geer

Reticulitermes speratus Kolbe

Oxidus gracilis C. L. Koch

Thereuronema hilgendorfi Verhoeff

Where the compounds of the formula (1) of the invention are actuallyapplied, they may be used singly without addition of any otheringredient. However, it is usual to incorporate carriers in order tomake easier application as a control chemical.

For preparation of the compounds of the invention, any specificrequirement is not necessary to formulate them into variouspreparations, such as emulsions, wettable powders, dusts, granules, finepowders, flowable preparations, microcapsules, oils, aerosols, smokingagents, poisonous feeds and the like, according to the procedures ofpreparing general agricultural chemicals well known in the art.

The term "carrier" used herein is intended to mean synthetic or natural,organic or inorganic materials which assist the effective ingredient toarrive at sites or portions to be treated and which are blended in orderto make easier storage, transport and handling of the effectivecompound.

Appropriate solid carriers include, for example, inorganic substancessuch as montmorilonite, kaolinite, diatomaceous earth, white clay, talc,vermiculite, gypsum, calcium carbonate, silica gel and ammonium sulfate,and organic substances such as soybean flour, saw dust, wheat flour,pectin, methyl cellulose, sodium alginate, vaseline, lanolin, liquidparaffin, lard and vegetable oils.

Suitable liquid carriers include, for example, aromatic hydrocarbonssuch as toluene, xylene, cumene and solvent naphtha, paraffinichydrocarbons such as kerosene and mineral oils, halogenated hydrocarbonssuch as methylene chloride, chloroform and carbon tetrachloride, ketonessuch as acetone, methyl ethyl ketone and cyclohexane, ethers such asdioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethyleneglycol dimethyl ether, diethylene glycol monomethyl ether and propyleneglycol monomethyt ether, esters such as ethyl acetate, butyl acetate andfatty acid glycerol ester, nitriles such as acetonitrile andpropionitrile, alcohols such as methanol, ethanol, n-propanol,isopropanol and ethylene glycol, dimethylformamide, dimethylsulfoxide,water and the like.

In order to reinforce the efficacy of the compounds of the formula (1)of the invention, the following adjuvants may be used singly or incombination, depending on the type of preparation, the manner ofapplication and the purpose.

Adjuvants used for the purpose of emulsification, dispersion, spreading,wetting, bonding and stabilization may include water-soluble bases suchas ligninsulfonates, nonionic surface active agents such asalkylbensenesulfonates, alkylsulfates, polyoxyethylene-alkyl aryl ethersand polyhydric alcohol esters, lubricants such as calcium stearate andwaxes, stabilizers such as isopropyl hydrogenphosphate, methylcellulose, carboxymethyl cellulose, casein, gum arabi, and the like. Itshould be noted that the adjuvants are not limited to those mentionedabove.

The derivatives of the formula (1) according to the invention maydevelop better insecticidal activity when used in combination of two ormore. If other physiologically active substances or chemicals are usedin combination, multipurpose compositions with good efficacy can beprepared with the possibility of developing a synergistic effct.

Examples of such physiologically active substances include: syntheticpyrethroid insecticide or pyrethrum extracts, such as allethrin,tetramethrin, resmethrin, phenothrin, furamethrin, permethrin,cypermethrin, deltamethrin, cyhalothrin, cyfluthrin, fenpropathrin,tralomethrin, cycloprothrin, flucythrinate, fluvalinate, acrinathrin,tefluthrin, silafluofen, bifenthrin, empenthrin, beta-cyfluthrin,zeta-cypermethrin and the like; organo-phosphate insecticides such asDDVP, cyanophos, fenthion, fenitrothion, dichlofenthion,tetrachlorvinphos, dimethylvinphos, chlorfenvinphos, propaphos,methyparathion, temephos, phoxim, acephate, isofenphos, salithion,DEP,EPN, ethion, mecarbam, pyridafenthion, diazinon, pirimiphos-methyl,etrimfos, isoxathion, quinalphos, chloropyriphos-methyl, chloropyriphos,phosalone, phosmet, methidathion, oxydeprofos, vamidothion, malathion,phenthoate, dimethoate, fomothion, thiomelon, ethylthiometon, phorate,terbufos, oxydeprofos, profenophos, prothiofos, sulprofos, pyraclofos,monocrotophos, naled, fosthiazate and the like; carbamate insectiscidessuch as NAC, MTMC, MIPC, BPMC, XMC, PHC, MPHC, ethiofencarb, bendiocarb,primicarb, carbosurfan, benfuracarb, methomyl, oxamyl, aldicarb and thelike: aryl propyl ether insecticides such as etofenprox, flufenprox,halfenprox and the like: aromatic alkane insecticides such as1-(3-phenoxyphenyl)-4-(4-ethoxyphenyl)-4-methylpentane,1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methylpentan and thelike; silyl ether insecticides such as silafluofen and the like:insecticidal natural substances such as nicotine-sulfate, polynactins,avermectin, milbemectin and the like; insecticides such as cartap,thiocyclam, bensultap, diflubenzuron, chlorfluazuron, teflubenzuron,triflumuron, flufenoxuron, novaluron, flucycloxuron, hexaflumuron,fluazuron, imidacloprid, nitenpyram, NI-25, pymetrozine, fipronil,buprofezin, fenoxycarb, pyriproxyfen, methoprene, hydroprene, kinoprene,endosulfan, diafenthiuron, triazuron. tebufenozide and the like;acaricides such as dicofol, CPCBS, BPPS, tetradifon, amitraz,benzoinate, fenothiocarb, hexythiazox, fenbutatin oxide, dienochlor,clofentezine, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen,agrimont and the like and other insecticides, acaricides, fungicides,nematocides, herbicides, plant regulators, fertilizers. soil improvingmaterials, molting inhivitors, JH activators, BT agents,micro-organisms-derived toxins, natural or synthetic insect hormonedisturbing agents, attractants, repellents, insectpathogenicmicroorganisms, and small animals and other agricultural chemicals.

Although the compounds of the formula (1) of the invention are stable tolight, heat and oxidation, antioxidants or UV absorbers may be added inappropriate amounts, if necessary, including, for example, phenolderivatives or bisphenol derivatives such as BHT(2,6-di-t-butyl-4-methylphenol), BHA (butylhydroxyanisole) and the like,arylamines or benzophenone compounds such as phenyl-α-naphthylamine,phenyl-β-naphthylamine, condensates of phenetidine and acetone, therebyobtaining more stable compositions.

The insecticide comprising the compound of the formula (1) of theinvention contains the compound in an amount of from 0.0000001 to 95wt.%, preferably from 0.0001 to 50 wt.%.

When the insecticide of the invention is applied, the effectiveingredient is used generally at a concentration of from 0.001 to 5,000ppm, preferably from 0.01 to 1,000 ppm. The application amount per 10ares is generally in the range of from 1 to 300 g of the effectiveingredient.

The present invention is more particularly described by way of thefollowing examples and reference examples.

Example 1 Preparation of1-[{(tetrahydro-3-furanyl)methyl}amino]-1-methylamino-2-nitroethylene(Compound No. 1):

A mixture comprising 7.0 g of (tetrahydro-3-furanyl)methylamine, 12.5 gof 1,1-bis(methylthio)-2-nitroethylene and 100 ml of acetonitrile wasrefluxed for 5 hours. The reaction mixture was concentrated under areduced pressure, and purified by silica gel column chromatography(eluent:ethyl acetate/hexane=1/1) to give 6.6 g of1-[{tetrahydro-3-furanyl)methyl}amino]-1-methylthio-2-nitroethylene.Then, a mixture comprising 4.0 g of the1-[{(tetrahydro-3-furanyl)methyl}amino]-1-methylthio-2-nitroethyleneobtained above, 6.0 ml of 40% methylamine in methanol solution, 20 ml of1N aqueous sodium hydroxide solution and 20 ml of ethanol was stirred atroom temperature for 5 hours. The resulting reaction mixture wasconcentrated under a reduced pressure, and purified by silica gel columnchromatography (eluent:ethyl acetate/methanol=9/1) to obtain 3.2 g of1-[{(tetrahydro-3-furanyl)methyl}amino]-1-methylamino-2-nitroethylene.

Example 2 Preparation of 1-[{(tetrahydro-3-furanyl)methyl}amino]-1-methylamino-2-nitroethylene (Compound No. 1):

A mixture comprising 1.79 g of 1-[{(tetrahydro-3-furanyl)methyl}amino-1-methylthio-2-nitroethylene, 1 ml of 40%methylamine in methanol solution and 30 ml of ethanol was stirred atroom temperature for 5 hours. The reaction mixture was concentratedunder a reduced pressure to give an oily matter. This was purified bycolumn chromatography to obtain 1.54 g of1-[{tetrahydro-3-furanyl)methyl}amino]-1-methylamino-2-nitroethylene.

Example 3 Preparation of1-[{(tetrahydro-3furanyl)methyl}amino]-1-ethylamino-2-nitroethylene(Compound No. 2):

A mixture comprising 0.51 g of1-[{(tetrahydro-3-furanyl)methyl}amino]-1-methylthio-2-nitroethylene, 1ml of 70% aqueous ethylamine solution and 10 ml of ethanol was stirredat room temperature for 5 hours. The reaction mixture was concentratedunder a reduced pressure to give an oily matter. This was purified bycolumn chromatography to obtain 0.50 g of1-[{tetrahydro-3-furanyl)methyl}amino]-1-ethylamino-2-nitroethylene.

Example 4 Preparation of1-[{(tetrahydro-3-furanyl)methyl}amino]-1-dimethylamino-2-nitroethylene(Compound No. 3):

A mixture comprising 4.0 g of1-[{(tetrahydro-3-furanyl)methyl}amino]-1-methylthio-2-nitroethylene, 10ml of 50% aqueous dimethylamine solution and 50 ml of acetonitrile wasstirred at room temperature for an hour. The reaction mixture wasconcentrated under a reduced pressure, and purified by silica gel columnchromatography (eluent:ethyl acetate/acetone=1/1) to obtain 2.8 g of1-[{(tetrahydro-3-furanyl)methyl}amino]-1-dimethylamino-2-nitroethylene.

Example 5 Preparation of1-[{(tetrahydro-3-furanyl)methyl}amino]-1-(1-pyrrolidinyl)-2-nitroethylene(Compound No. 4):

A mixture comprising 1.2 g of1-[{(tetrahydro-3-furanyl)methyl}amino]-1-methylthio-2-nitroethylene,1.5 ml of pyrrolidine and 15 ml of acetonitrile was stirred at roomtemperature for an hour. The reaction mixture was concentrated under areduced pressure, and purified by silica gel column chromatography(eluent:ethyl acetate/acetone=1/1) to obtain 0.92 g of1-[{(tetrahydro-3-furanyl)methyl}amino]-1-(1-pyrrolidinyl)-2-nitroethylene.

Example 6 Preparation of1-[N-{(tetrahydro-3-furanyl)methyl}-N-methylamino]-1-methylamino-2nitroethylene(Compound No. 6):

A mixture comprising 1.42 g of (tetrahydro-3-furanyl)methyl tosylate,0.15 g of sodium iodide, 1.70 g of potassium carbonate and 18 ml of 40%methylamine in methanol solution was heated under reflux for 5 hours.After separation of insoluble matters by filtration, the reaction fluidwas concentrated under a reduced pressure to obtain crudeN-{(tetrahydro-3-furanyl)methyl}-N-methylamine. To this were added 1.00g of 1,1-bis(methylthio)-2-nitroethylene and 14 ml of acetonitrile. Themixture was refluxed for 4 hours. The resultant reaction fluid wasconcentrated under a reduced pressure, and purified by silica gel columnchromatography.(eluent:ethyl acetate/hexane=1/1) to obtain 1.00 g of1-[N-{(tetrahydro-3-furanyl)methyl}-N-methylamino]-1-methylthio-2-nitroethylene.A mixture comprising 0.9 g of the1-[N-{(tetrahydro-3-furanyl)methyl}methylamino]-1-methylthio-2-nitroethyleneobtained above and 15 ml of 40% methylamine in methanol solution wasstirred for 45 minutes at room temperature. The reaction fluid wasconcentrated under a reduced pressure, and purified by silica gel columnchromatography (eluent:ethyl acetate/methanol=3/1) to obtain 0.45 g of1-[N-{(tetrahydro-3-furanyl)methyl}-N-methylamino]-1-methylamino-2-nitroethylene.

Example 7 Preparation of1-[N-{(tetrahydro-3-furanyl)methyl}-N-ethylamino]-1-methylamino-2-nitroethylene(Compound No. 12):

A mixture comprising 4.09g of (tetrahydro-3-furanyl)methyl tosylate, 17ml of 70% aqueous ethylamine solution and 8.2 ml of 2N aqueous sodiumhydroxide solution was stirred at 75° C. for 6 hours. The reaction fluidwas concentrated under a reduced pressure to obtain crudeN-{(tetrahydro-3-furanyl)methyl}-N-ethylamine. To this were added 2.00 gof 1,1-bis(methylthio)-2-nitroethylene and 20 ml of acetonitrile. Theresulting mixture was refluxed for 3 hours. The reaction fluid wasconcentrated under a reduced pressure, and purified by silica gel columnchromatography (eluent:ethyl acetate/hexane=1/2) to obtain 0.81 g of1-[N-{(tetrahydro-3-furanyl)methyl}-N-ethylamino]-1-methylthio-2nitroethylene.

A mixture comprising 2.5 g of the1-[N-{(tetrahydro-3-furanyl)methyl}-N-ethylamino]-1-methylthio-2-nitroethyleneobtained above and 6 ml of 40% methylamine in methanol solution wasstirred for 2 hours at room temperature. The reaction fluid wasconcentrated under a reduced pressure, and purified by silica gel columnchromatography (eluent:ethyl acetate/methanol=7/1) to obtain 2.0 g of1-[N-{(tetrahydro-3-furanyl)methyl}-N-ethylamino]-1-methylamino-2-nitroethylene.

Example 8 Preparation of1-[N-{(tetrahydro-3-furanyl)methyl}-N-propylamino]-1-methylamino-2-nitroethylene(Compound No. 15):

A mixture comprising 3.00 g of (tetrahydro-3-furanyl)methyl tosylate,0.20 g of sodium iodide, 3.50 g of potassium carbonate, 4.00 g ofpropylamine and 30 ml of ethanol was refluxed for 8 hours. Afterseparation of insoluble matters by filtration, the reaction fluid wasconcentrated under a reduced pressure to obtain crudeN-{(tetrahydro-3-furanyl)methyl}propylamine. To this were added 1.90 gof 1,1-bis(methylthio)-2-nitroethylene and 16 ml of acetonitrile. Theresulting mixture was refluxed for 4 hours. The reaction fluid wasconcentrated under a reduced pressure, and purified by silica gel columnchromatograpy (eluent:ethyl acetate/hexane=1/2) to obtain 1.00 g of1-[N-{(tetrahydro-3-furanyl)methyl}-N-propylamino]-1-methylthio-2-nitroethylene.A mixture comprising 0.25 g of the1-[N-{(tetrahydro-3-furanyl)methyl}-N-propylamino]-1-methylthio-2-nitroethyleneobtained above and 3 ml of 40% methylamine in methanol solution wasstirred for 40 minutes at room temperature. The reaction fluid wasconcentrated under a reduced pressure, and purified by silica gel columnchromatography (eluent:ethyl acetate/methanol=7/1) to obtain 0.22 g of1-[N-{(tetrahydro-3-furanyl)methyl}propylamino]-1-methylamino-2-nitroethylene.

Example 9 Preparation of1-[N-{(tetrahydro-3-furanyl)methyl}-N-propylamino]-1-ethylamino-2-nitroethylene (Compound No. 16):

A mixture comprising 0.25 g of1-[N-{(tetrahydro-3-furanyl)methyl}-N-propylamino]-1-methylthio-2-nitroethyleneand 1 ml of 70% aqueous ethylamine solution was stirred for an hour atroom temperature. After concentration of the mixture under a reducedpressure, the reaction fluid was purified by silica gel columnchromatography (eluent: ethyl acetate/methanol=7/1) to obtain 0.25 g of1-[N-{(tetrahydro-3-furanyl)methyl}-N-propylamino]-1-ethylamino-2-nitroethylene.

Example 10 Preparation of1-{(tetrahydro-3-furanyl)methyl}-2-nitro-3-methylguanidine (Compound No.20):

A mixture comprising 10.0 g of (tetrahydro-3-furanyl)methanol, 29.5 g oftrifluoromethanesulfonic anhydride, 10.0 g of pyridine and 200 ml ofdichloromethane was stirred for an hour at room temperature. Water waspoured into the reaction solution to separate the organic layer, whichwas washed with 1N hydrochloric acid, water and a saturated salinesolution, dried, and concentrated to obtain 20 g of3-tetrahydro-furanylmethyl triflate. 3.25 g of 60% sodium hydride wereadded to 12.5 g of 1,5-dimethyl-2-nitroiminohexahydro-1,3,5-triazine and60 ml of DMF at room temperature, followed by stirring for an hour. 20.0g of the 3-tetrahydrofuranylmethyl triflate were added thereto, and themixture was stirred at 50° C. for 2 hours. After cooling the mixture toroom temperature, 50 ml of 2N hydrochloric acid were added thereto,followed by stirring at 50° C. for 2 hours. The resultant mixture wasneutralized with sodium bicarbonate and extracted with dichloromethane,and the extract was dried and concentrated. The residue thus obtainedwas purified by silica gel column chromatography (eluent:ethylacetate/hexane=1/1) to obtain 7.8 g of1-{(tetrahydro-3-furanyl)methyl}-2-nitro-3-methylguanidine.

Example 11 Preparation ofN-{(tetrahydro-3-furanyl)methyl}-N-(methyl)nitroguanidine (Compound No.26):

A mixture comprising 0.71 g of (tetrahydro-3-furanyl)methyl tosylate,0.08 g of sodium iodide, 0.85 g of potassium carbonate and 9 ml of 40%methylamine in methanol solution was refluxed for 5 hours. Afterseparating insoluble matters by filtration, the reaction fluid wasconcentrated under a reduced pressure to obtain crudeN-{(tetrahydro-3-furanyl)methyl)methylamine. To this were added 0.38 gof S-methyl-N-(nitro)isothiourea and 7 ml of acetonitrile, followed byrefluxing for 5 hours. The reaction fluid was concentrated under areduced pressure, and purified by silica gel column chromatography(eluent: ethyl acetate/hexane=1/1) to obtain 0.10 g ofN-{(tetrahydro-3-furanyl)methyl}-N-(methyl)nitroguanidine.

Example 12 Preparation of1-{(tetrahydro-3-furanyl)methyl}-2-nitro-3-methylguanidine (Compound No.20):

A mixture comprising 0.7 g of1-{(tetrahydro-3-furanyl)methyl}-2-(nitroimino)-3,5-dimethylhexahydro-1,3,5-triazine,5 ml of 1N hydrochloric acid and 5 ml of ethanol was stirred at 40° C.for an hour. The reaction fluid was concentrated under a reducedpressure and purified by column chromatography to obtain 0.4 g of1-{(tetrahydro-3-furanyl)methyl}-2-nitro-3-methylguanidine.

Example 13 Preparation of1-{(tetrahydro-3-furanyl)methyl}-1-ethyl-2-nitro-3-methylguanidine(Compound No. 29):

A mixture comprising 5.5 g ofN-{(tetrahydro-3-furanyl)methyl}-N-ethylamine, 3.0 g ofS-methyl-N-nitro-N'-methyisothiourea, 30 ml of ethanol and 0.5 g of DMAPwas refluxed for 4 hours. Then, the reaction fluid was concentratedunder a reduced pressure to obtain an oily matter, which was purified bycolumn chromatography. 1.1 g of1-{(tetrahydro-3-furanyl)methyl}-1-ethyl-2-nitro-3-methylguanidine wereobtained.

Example 14 Preparation ofN-(tetrahydro-3-furanyl)methyl-N'-cyano(methylthio)formamidine (CompoundNo. 50):

A mixture comprising 0.61 g of (tetrahydro-3-furanyl)methylamine, 1.10 gof 90% S,S'-dimethyl-N-cyanocarbonate and 10 ml of acetonitrile wasrefluxed for 5 hours. The reaction fluid was concentrated under areduced pressure and purified by silica gel column chromatography(eluent: ethyl acetate/hexane=1/1) to obtain 0.40 g ofN-(tetrahydro-3-furanyl)methyl-N'-cyano(methylthio)formamidine.

Example 15 Preparation ofN-cyano-N'-{(tetrahydro-3furanyl)methyl}acetamidine (Compound No. 55):

A mixture comprising 0.6 g of (tetrahydro-3-furanyl)methylamine, 0.7 gof ethyl N-cyanoacetamidate and 10 ml of ethanol was stirred for 3 hoursat room temperature. The reaction fluid was concentrated under a reducedpressure and purified by silica gel column chromatography (eluent: ethylacetate) to obtain 0.40 g ofN-cyano-N'-{(tetrahydro-3-furanyl)methyl}acetamidine.

Example 16 Preparation ofN-cyano-N'-{(tetrahydro-3-furanyl)methyl}-N-methylacetamidine (CompoundNo. 51):

A mixture comprising 1.0 g ofN-{(tetrahydro-3-furanyl)methyl}-N-methylamine, 0.4 g of ethylN-cyanoacetamidate and 10 ml of ethanol was stirred for 7 hours at roomtemperature. The reaction fluid was concentrated under a reducedpressure and purified by silica gel column chormatography (eluent: ethylacetate) to obtain 0.38 g ofN-cyano-N'-{(tetrahydro-3-furanyl)methyl}-N-methylacetamidine.

Example 17 Preparation ofN-[4-{(2-methyl)tetrahydrofuranyl}methyl]-N'-methyl-N"-nitroguanidine(Compound No. 58):

A solution of 2.91 g of trifluoromethanesulfonic anhydride in 10 ml ofdichloromethane was added dropwise over 5 minutes under ice-cooling to asolution of 1.00 g of 2-methyl-4-hydroxymethyltetrahydrofuran and 1.05 gof triethylamine in 50 ml of dichloromethane. The reaction fluid wasstirred under ice-cooling for 30 minutes and at room temperature for 5hours. The reaction fluid was concentrated under a reduced pressure toobtain an oily matter. This was added as a solution in 5 ml ofdimethylformamide at room temperature to a reaction mixture, which hadbeen obtained by adding at room temperature a solution of 1.24 g of1-methyl-2-nitroimino-5-methyl-1,3,5-triazine in 5 ml ofdimethylformamide to a suspension of 0.32 g of sodium hydride (60%) in 5ml of dimethylformamide and stirring the mixture at 60° C. for 30minutes, followed by stirring at 60° C. for 4 hours. 7.2 ml ofhydrochloric acid (2M) was added to the resultant reaction fluid,followed by stirring at 60° C. for 3 hours. After cooling the reactionfluid to room temperature, ethyl acetate was added thereto. Theresultant reaction fluid was washed with water, and the organic layerwas dried over anhydrous magnesium sulfate. The organic layer wasconcentrated under a reduced pressure to obtain an oily matter, whichwas purified by silica gel column chromatography (eluent:ethyl acetate)to obtain 77 mg ofN-[4-{(2-methyl)tetrahydrofuranyl}methyl]-N'-methyl-N"-nitroguanidine asa red-brown oily matter.

Example 18 Preparation ofN-[4-{2-methyl)tetrahydrofuranyl}methyl]-N'-methyl-N"-nitroguanidine(Compound No. 58):

A solution of 4.19 g of triethylamine in 5 ml of dichloromethane wasadded dropwise under ice-cooling over 10 minutes to a solution of 5.70 gof {4-(2-methyl)tetrahydrofurylmethyl}amine hydrochloride and 9.07 g ofS-methyl-N-nitro-N'-phthaloylisothiourea in 45 ml of dichloromethane.After stirring the reaction fluid for 2 hours under ice-cooling,insoluble matters were separated by filtration and the filtrate waswashed with an aqueous hydrochloric acid solution (1M) and a saturatedsaline solution. The organic layer was dried over anhydrous magnesiumsulfate and concentrated under a reduced pressure to obtain an oilymatter. This was purified by silica gel column chromatography(eluent:hexane/ethyl acetate=1/1) to obtain 7.04 g ofS-methyl-N-{(4-(2-methyl)tetrahydrofurylmethyl}-N'-nitroisothiourea as acolorless oily matter. To a solution of 9.39 g of theS-methyl-N-{(4-(2-methyl)tetrahydrofurylmethyl}-N'-nitroisothioureaobtained in this manner in 30 ml of methanol were added 3.43 g of methylamine (as 40% methanol solution) at room temperature, followed bystirring for 1.5 hours at room temperature. The reaction fluid wasconcentrated under a reduced pressure to obtain an oily matter, whichwas purified by silica gel column chromatography (eluent:ethyl acetate)to obtain 7.77 g ofN-[4-{(2-methyl)tetrahydrofuranyl}methyl]-N'-methyl-N"-nitroguanidine asa colorless oily matter.

Example 19 Preparation of1-{(tetrahydro-3-furanyl)methyl}-1,2-dicyclohexylcarbonyl-2-methyl-3-nitroguanidine(Compound No. 33):

0.6 g of 1-{(tetrahydro-3-furanyl)methyl}-2-methyl-3-nitroguanidine, 0.3g of sodium hydride and 10 ml of acetonitrile were stirred at roomtemperature until foaming does not occur. A solution of 0.7 g ofcyclohexylcarbonyl chloride in 5 ml of acetonitrile was added theretodropwise under ice-cooling, followed by stirring for 30 minutes at roomtemperature. The reaction fluid was filtrated and the filtrate wasconcentrated. The oily matter thus obtained was purified by a silica gelcolumn (eluent:ethyl acetate/hexane=1/1) to obtain 0.87 g of1-{(tetrahydro-3-furanyl)methyl}-1,2-dicyclohexylcarbonyl-2-methyl-3-nitroguanidine.

Example 20 Preparation of1-{(tetrahydro-3-furanyl)methyl}-1,2-diethylcarbonyl-2-methyl-3-nitroguanidine(Compound No. 35):

0.6 g of 1-{(tetrahydro-3-furanyl)methyl}-2-methyl-3-nitroguanidine, 0.3g of sodium hydride and 10 ml of acetonitrile were stirred at roomtemperature until foaming does not occur. A solution of 1.0 g ofpropionyl chloride in 5 ml of acetonitrile was added thereto dropwiseunder ice-cooling, followed by stirring for 30 minutes at roomtemperature. The reaction fluid was filtrated and the filtrate wasconcentrated. The oily matter thus obtained was purified by a silica gelcolumn (eluent:ethyl acetate/hexane=1:1) to obtain 0.51 g of1-{(tetrahydro-3-furanyl)methyl}-1,2-diethylcarbonyl-2-methyl-3-nitroguanidine.

Example 21 Preparation of 1-{(tetrahydro-3-furanyl)methyl}-1,2-dimethoxycarbonyl-2-methyl-3nitroguanidine (Compound No.38):

1.0 g of 1-{(tetrahydro-3-furanyl)methyl}-2-methyl- 3-nitroguanidine,0.5 g of sodium hydride and 10 ml of acetonitrile were stirred at roomtemperature until foaming does not occur. A solution of 1.5 ml of methylchloroformate in 5 ml of acetonitrile was added thereto dropwise between-5° and 3° C., followed by stirring for 30 minutes at room temperature.The reaction fluid was filtrated and the filtrate was concentrated. Theoily matter thus obtained was purified by a silica gel column(eluent:ethyl acetate/hexane=1/1) to obtain 1.22 g of1-{(tetrahydro-3-furanyl)methyl}-1,2-dimethoxycarbonyl-2-methyl-3-nitroguanidine.

Example 22 Preparation of1-{(tetrahydro-3-furanyl)methyl}-1,2-dibenzoyl-2-methyl-3-nitroguanidine(Compound No. 40):

1.0 g of 1-{(tetrahydro-3-furanyl)methyl}-2-methyl-3-nitroguanidine, 0.5g of sodium hydride and 10 ml of dimethylformamide were stirred at roomtemperature until foaming does not occur, and 1 ml of benzoyl chloridewas added thereto dropwise, followed by stirring for 30 minutes at roomtemperature. Water was poured into the reaction fluid, the aqueoussolution was extracted with ethyl acetate, and the extract was washedwith water, dried, and concentrated. The oily matter thus obtained waspurified by a silica gel column (eluent:ethyl acetate/hexane=1/2) toobtain 0.15 g of1-{(tetrahydro-3-furanyl)methyl}-1,2-dibenzoyl-2-methyl-3-nitroguanidine.

Reference Example 1 Preparation of1-{(tetrahydro-3-furanyl)methyl}-2-(nitroimino)-3,5-dimethylhexahydro-1,3,5-triazine(Compound No. 2):

A mixture comprising 3.00 g of1-{(tetrahydro-3-furanyl)methyl}-2-(nitroimino)-5-methylhexahydro-1,3,5-triazine,0.54 g of sodium hydride and 40 ml of DMF was stirred at 50° C. for 30minutes. Then, 2.08 g of methyl iodide were added thereto, followed bystirring at 70° C. for 2 hours. The reaction fluid was poured into asaturated saline solution and the mixture was extracted with methylenechloride several times. The methylene chloride solution was dried overanhydrous sodium sulfate and concentrated under a reduced pressure. Thecrude oily matter thus obtained was purified by column chromatography toobtain 1.43 g of1-{(tetrahydro-3-furanyl)methyl}-2-(nitroimino)-3,5-dimethylhexahydro-1,3,5-triazine.

Reference Example 2 Preparation of (tetrahydro-3-furanyl)methylamine(Compound No. B1):

1 ml of 25% aqueous NaOH solution was added to a suspension of 1.50 g ofN-{(tetrahydro-3-furanyl)methyl}phthalimide in 8 ml of water, followedby stirring at 70° C. for 3 hours. The reaction fluid was added dropwiseto an aqueous 10% HCl solution at 70° C. and the mixture was stirred for5 hours at the same temperature. While the reaction fluid was hot, 12 mlof toluene was added thereto. The aqueous layer was separated, madeweakly alkaline with an aqueous 50% NaOH solution, and extracted withdichloromethane. The extract was dried and concentrated under a reducedpressure to obtain 0.55 g of (tetrahydro-3-furanyl)methaylamine.

Reference Example 3 Preparation of{4-(2-methyl)tetrahydrofurylmethyl}amine hydrochloride (Compound No.B4):

(1) A solution of 14.1 g of methanesulfonyl chloride in 10 ml oftetrahydrofuran was added dropwise under ice-cooling over 30 minutes toa solution of 13.0 g of {4-(2-methyl)tetrahydrofuran}methanol and 12.5 gof triethylamine in 85 ml of tetrahydrofuran. The reaction fluid wasstirred for an hour under ice-cooling and for 2 hours at roomtemperature. Then, insoluble matters were separated by filtration andthe filtrate was concentrated under a reduced pressure to obtain an oilymatter. A suspension of this oily matter and 20.7 g of potassiumphthalimide in 115 ml of dimethylformamide was stirred at 80° C. for 3hours. The reaction fluid was cooled to room temperature, to which ethylacetate was added, and the mixture was washed with water. The organiclayer was dried over anhydrous magnesium sulfate and concentrated undera reduced pressure to obtain an oily matter. This was purified by silicagel column chromatography (eluent:hexane/ethyl acetate=2/1) andrecrystallization (from ethylacetate and hexane) to obtain 22.1 g ofN-{4-(2-methyl)tetrahydrofurylmethyl}phthalimide as colorless crystals.

(2) A solution of 21.0 g of N-{4-(2-methyl)tetrahydrofurylmethyl}phthalimide and 4.86 g of hydrazine monohydrate(98%) in 100 ml of ethanol was refluxed for 2 hours. The reaction fluidwas cooled to room temperature, to which 8.6 ml of concentratedhydrochloric acid were added, and the mixture was stirred for 1.5 hoursat room temperature. Insoluble matters were separated by filtration andthe filtrate was concentrated under a reduced pressure to removeethanol. An aqueous sodium hydroxide solution was added to the resultingfiltrate to make it alkaline. The aqueous solution thus obtained wasextracted with dichloromethane, and the organic layer was dried overanhydrous potassium carbonate and concentrated under an atmosphericpressure to obtain an oily matter. 60 ml of ethyl acetate was added tothe oily matter, followed by addition of 30 ml of a solution of hydrogenchloride in ethyl acetate (4M) under ice-cooling. The crystals thusprecipitated out were separated by filtration to obtain 5.70 g of{4-(2-methyl)tetrahydrofurylmethyl}amine hydrochloride as colorlesscrystals.

Reference Example 4 Preparation of{2-methyl-(4-tetrahydrofuran)}methanol (Compound No. C1):

(1) A solution of 25.0 g of diethyl malonate in 5 ml ofdimethylformamide was added dropwise under ice-cooling over 20 minutesto a suspension of 6.55 g of sodium hydride in 90 ml ofdimethylformamide. The reaction fluid was stirred for an hour underice-cooling, to which a solution of 17.3 g of chloroacetone in 5 ml ofdimethylformamide was added, and the mixture was stirred for an hourunder ice-cooling and for 6 hours at room temperature. Ethyl acetate wasadded to the reaction fluid and the mixture was washed with water. Theorganic layer was dried over anhydrous magnesium sulfate. An oily matterobtained by concentrating the organic layer under a reduced pressure wasdistilled under vacuum to obtain 14.8 g of diethyl 2-oxopropylmalonateas a yellow oily matter.

δ_(TMS) CDCl₃ (ppm): 1.27 (6H, t, J=7.3), 2.21 (3H, s), 3.06 (2H, d,J=7.3), 3.86 (1H, t, J=7.3), 4.20 (4H, q, J=7.3) ν_(MAX), neat(cm⁻¹):2985, 2940, 1732, 1467, 1448, 1406, 1370, 1332, 1273,. 1237, 1161, 1098,1050, 1026, 867

b.p.: 125°-135° C. (5 mmHg)

(2) A solution of 11.4 g of diethyl 2-oxopropylmalonate in 30 ml oftetrahydrofuran was added dropwise under ice-cooling over 20 minutes toa suspension of 5.00 g of lithium aluminum hydride in 100 ml oftetrahydrofuran. The reaction fluid was stirred for an hour underice-cooling and for 4.5 hours at room temperature, and 10 ml of waterwas added thereto dropwise under ice-cooling over 20 minutes. Thereaction fluid was refluxed for an hour and filtrated. The unfilteredsolid was suspended in 200 ml of ethanol and the suspension wasrefluxed. The suspension was filtrated, and the filtrate combined withthe foregoing filtrate was concentrated under a reduced pressure toobtain 7.08 g of 2-hydroxymethyl-1,4-pentanediol as a colorless oilymatter.

ν_(MAX), neat (cm⁻¹): 3313, 2969, 2928, 1706, 1457, 1420, 1375, 1091,1050

(3) A mixture comprising 7.08 g of 2-hydroxy-methyl-1,4-pentanediol and7.3 ml of phosphoric acid (85%) was stirred at 120° C. for 3 hours. Thereaction mixture was cooled to room temperature, to which water wasadded, and the mixture was extracted with dichloromethane. The organiclayer was dried over anhydrous magnesium sulfate and concentrated undera reduced pressure. An oily matter thus obtained was distilled undervacuum to obtain 2.69 g of {2-methyl-(4-tetrahydrofuran)m}ethanol as acolorless oily matter.

Reference Example 5 Preparation ofN-{(tetrahydro-3furanyl)methyl}phthalimide (Compound No. D4):

A mixture comprising 30.0 g of (tetrahydro-3-furanyl)methyl tosylate,23.0 g of potassium phthalimide and 150 ml of DMF was stirred at 80° C.for 8 hours. Water was poured into the reaction mixture, and crystalsprecipitated out was separated by filtration to obtain 27.0 g ofN-{(tetrahydro-3-furanyl)methyl}phthalimide.

Reference Example 6 Preparation of (tetrahydro-3-furanyl)methyl tosylate(Compound No. D5):

A mixture comprising 50 g of (tetrahydro-3-furanyl)methanol, 95 g oftosyl chloride, 52 g of triethylamine and 450 ml of THF was refluxed for8 hours. After separation of insolubles by filtration, the reactionfluid was concentrated under a reduced pressure, and the residue waspurified by silica gel column chromatography (eluent:ethylacetate/hexane=1/7) to obtain 114.5 g of (tetrahydro-3-furanyl)methyltosylate.

Reference Example 7 Preparation of (tetrahydro-3-furanyl)methyl bromide(Compound No. D6):

To a mixture comprising 10 g of phosphorus tribromide, 0.8 g of pyridineand 100 ml of ether were added dropwise 10 g of(tetrahydro-3-furanyl)methanol over 30 minutes. The resulting mixturewas stirred for 5.5 hours. The reaction fluid was concentrated under areduced pressure, and the residue was purified by silica gel columnchromatography (eluent: ethyl acetate/hexane=1/1) to obtain 8.6 g of(tetrahydro-3-furanyl)methyl bromide.

Specific examples of the compounds of the formula (1) prepared inaccordance with the same procedures as described in Examples 1 through22 and Reference Examples 1 through 7 and examples of intermediatesthereof are illustrated in Tables 1-4 along with the compounds of theExamples and Reference Examples.

                  TABLE 1                                                         ______________________________________                                        Compound                                                                      No.                                                                           R.sub.1                                                                       R.sub.2 Physical Properties                                                   ______________________________________                                        (Z═CH--NO.sub.2,                                                          X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.5 =X.sub.6 =X.sub.7 =H in           formula (1))                                                                  1       δ.sub.TMS (DMSO-d.sub.6)(ppm):1.51-1.63(1H, m),                 H       1.90-2.04(1H, m)                                                      NHMe    2.42-2.54(1H, m), 2.67-2.91(3H, br), 3.05-3.25(2H, br)                        3.40-3.47(1H, br), 3.59-3.81(3H, br),                                         6.45-6.55(1H, br)                                                             7.15-7.28(1H, br), 9.90-10.1(1H, br)                                          ν.sub.max (KBr)(cm.sup.-1):3186, 1637, 1584, 1222, 997                     m.p.:140.0-141.0°C.                                            2       δ.sub.TMS (CDCl.sub.3)(ppm):1.21-1.41(3H, m),                   H       1.65-1.82(1H, m)                                                      NHEt    2.05-2.25(1H, m), 2.50-2.71(1H, m), 3.02-3.35(4H, m)                          3.55-4.01(4H, m), 5.41-5.82(1H, br), 6.58(1H, s),                             10.00-10.90(1H, br)                                                           ν.sub.max (neat)(cm.sup.-1):3274, 1615, 1233                               n.sub.D (18.4°C.):1.5455                                       3       δ.sub.TMS (CDCl.sub.3)(ppm):1.57-1.69(1H, m),                   H       2.11-2.29(1H, m)                                                      NMe.sub.2                                                                             2.45-2.67(1H, m), 2.94(6H, s), 3.19-3.35(2H, m),                              3.56(1H, dd, J=5.2Hz, J=8.8Hz), 3.70-3.99(3H, m),                             6.51(1H, s)                                                                   9.63(1H, br)                                                                  ν.sub.max (neat)(cm.sup.-1):3261, 1615, 1515, 1435, 1271           4       δ.sub.TMS (CDCl.sub.3)(ppm):1.60-1.72(1H, m),                   H       1.96-2.01(4H, m)                                                      pyrolidinyl                                                                           2.12-2.24(1H, m), 2.51-2.67(1H, m), 3.26-3.37(2H, m)                          3.41-3.46(4H, m), 3.59(1H, dd, J=5.2Hz, J=8.8Hz),                             3.71-3.95(3H, m), 6.60(1H, s), 10.18(1H, br)                                  ν.sub.max (neat)(cm.sup.-1):3267, 1597, 1457, 1270, 1235           5       δ.sub.TMS (CDCl.sub.3)(ppm):1.52-1.65(1H, m),                   Me      2.01-2.14(1H, m)                                                      H       2.58-2.79(1H, m), 2.88(3H, s), 3.33(2H, d, J=7.3Hz),                          3.49-3.54(1H, m), 3.73-3.83(2H, m), 3.89-3.97(1H, m),                         6.63(1H, d, J=10.3Hz), 8.14(1H, d, J=10.3Hz)                                  ν.sub.max (neat)(cm.sup.-1):1624, 1302, 1252                       6       δ.sub.TMS (CDCl.sub.3)(ppm):1.48-1.58(1H, m),                   Me      2.01-2.12(1H, m)                                                      NHMe    2.61-2.70(1H, m), 2.93(3H, s), 3.01(3H, d, J=5.1Hz),                          3.20(2H, dd, J=1.5Hz, J=8.8Hz),                                               3.48(1H, dd, J=5.1Hz, J=8.8Hz)                                                3.71-3.82(2H, m), 3.89(1H, dt, J=5.1Hz, J=8.8Hz),                             6.53(1H, s), 9.73(1H, br)                                                     ν.sub.max (neat)(cm.sup.-1):3420, 1616, 1437, 1220                         n.sub.D (21.4°C.):1.5698                                       7       δ.sub.TMS (CDCl.sub.3, ppm):1.26(3H, t, J=7.3),                 H       1.25-1.35(2H, m)                                                      N(Me)Bu-n                                                                             1.55-1.68(3H, m), 2.04-2.17(1H, m), 2.50-2.64(1H, m),                         2.89(3H, s), 3.15-3.28(2H, m), 3.38(2H, t, J=7.3),                            3.56(1H, dd, J=5.1, J=8.8), 3.70-3.94(3H, m),                                 6.53(1H, s), 9.71(1H, br.)                                                    ν.sub.max (neat, cm.sup.-1):3276, 1682, 1560, 1254                 8       δ.sub.TMS (CDCl.sub.3)(ppm):1.01(3H, t, J=7.3Hz),               Me      1.47-1.59(1H, m)                                                      NHPr-n  1.65-1.78(2H, m), 1.98-2.10(1H, m),                                           2.65(1H, septet, J=6.6Hz), 2.92(3H, s),                                       3.18-3.26(4H, m), 3.49(1H, dd, J=5.1Hz, J=8.1Hz),                             3.70-3.81(2H, m), 3.89(1H, dt, J=5.1Hz, J=8.1Hz)                              6.52(1H, s), 9.60(1H, br)                                                     ν.sub.max (KBr)(cm.sup.-1):3430, 1588, 1235                        9       δ.sub.TMS (CDCl.sub.3, ppm):1.50-1.62(1H, m),                   Me      1.95-2.12(1H, m)                                                      NHCH.sub.2 -                                                                          2.38(1H, t, J=2.2Hz), 2.66(1H, septet, J=6.6Hz),                      proparg-                                                                              2.96(3H, s), 3.26(1H, dd, J=5.1Hz, J=8.1Hz),                          yl      3.49(1H, dd, J=5.1Hz, J=8.1Hz), 3.72-3.94(4H, m),                             4.03(2H, dd, J=2.2Hz, J=6.6Hz)                                                6.51(1H, s), 9.57(1H, br.)                                                    ν.sub.max (neat, cm.sup.-1):3430, 2170, 1586, 1332, 1239                   n.sub.D (20.7°C.):1.5682                                       10      δ.sub.TMS (CDCl.sub.3, ppm):1.46-1.60(1H, m),                   Me      1.99-2.07(1H, m), 2.57-2.67(1H, m), 2.92(3H, s),                      NHCH.sub. 2 -                                                                         3.20(2H, dd, J=3.7Hz, J=8.1Hz)                                        CH.sub.2 OCH.sub.3                                                                    3.38-3.49(3H, m), 3.41(3H, s), 3.58(2H, t, J=5.1Hz),                          3.71-3.82(2H, m), 3.88(1H, dt, J=5.1Hz, J=8.1Hz),                             6.51(1H, s)                                                                   9.53(1H, br.)                                                                 ν.sub.max (neat, cm.sup.-1):3261, 1587, 1251                       11      δ.sub.TMS (CDCl.sub.3, ppm):1.42-1.57(1H, m),                   Me      2.00-2.12(1H, m)                                                      NMe.sub.2                                                                             2.59-2.71(1H, m), 2.95(6H, s), 2.96(3H, s),                                   3.17-3.25(2H, m), 3.42(1H, dd, J=5.1, J=8.8),                                 3.68-3.87(3H, m), 6.34(1H, s)                                                 ν.sub.max (neat, cm.sup.-1):1524, 1403, 1256                       12      δ.sub.TMS (CDCl.sub.3)(ppm):1.20(3H, t, J=7.3Hz),               Et      1.47-1.62(1H, m)                                                      NHMe    1.97-2.10(1H, m), 2.54-2.67(1H, m),                                           3.01(3H, d, J=5.1Hz)                                                          3.05-3.17(2H, m), 3.25(2H, q, J=7.3Hz),                                       3.49(1H, dd, J=5.1Hz, J=8.1Hz),                                               3.69-3.79(2H, m), 3.89(1H, dt, J=5.1Hz, J=8.1Hz),                             6.55(1H, s), 9.89(1H, br)                                                     ν.sub.max (neat)(cm.sup.-1):3422, 1602, 1517, 1236                 13      δ.sub.TMS (CDCl.sub.3)(ppm):1.19(3H, t, J=7.3Hz),               Et      1.34(3H, t, J=7.3Hz), 1.47-1.59(1H, m),                               NHEt    1.97-2.09(1H, m), 2.62(1H, septet, J=6.6Hz),                                  3.08-3.17(2H, m), 3.20-3.36(4H, m),                                           3.48(1H, dd, J=5.1Hz, J=8.1Hz), 3.66-3.82(2H, m),                             3.88(1H, dt, J=5.1Hz, J=8.1Hz), 6.53(1H, s),                                  9.69(1H, br)                                                                  ν.sub.max (neat)(cm.sup.-1):3444, 1591, 1235                       14      δ.sub.TMS (CDCl.sub.3)(ppm):1.01(3H, t, J=7.3Hz),               Et      1.19(3H, t, J=7.3Hz), 1.50-1.78(3H, m),                               NHPr-n  1.94-2.08(1H, m), 2.62(1H, septet, J=6.6Hz),                                  3.13(2H, dq, J=5.1Hz, J=7.3Hz), 3.20-3.31(4H, m)                              3.48(1H, dd, J=5.1Hz, J=8.1Hz), 3.69-3.78(2H, m),                             3.88(1H, dt, J=5.1Hz, J=8.1Hz), 6.54(1H, s),                                  9.76(1H, br)                                                                  ν.sub.max (KBr)(cm.sup.-1):3430, 1589, 1223                        15      δ.sub.TMS (CDCl.sub.3)(ppm):0.91(3H, t, J=7.3Hz),               Pr-n    1.47-1.66(3H, m)                                                      NHMe    1.97-2.07(1H, m), 2.63(1H, septet, J=6.6Hz),                                  3.00(3H, d, J=5.1Hz, 3.11-3.18(4H, m),                                        3.48(1H, dd, J=5.1Hz, J=8.1Hz)                                                3.69-3.84(2H, m), 3.88(1H, dt, J=5.1Hz, J=8.8Hz),                             6.55(1H, s), 9.88(1H, br)                                                     ν.sub.max (neat)(cm.sup.-1):3258, 1593, 1236                       16      δ.sub.TMS (CDCl.sub.3)(ppm):0.90(3H, t, J=7.3Hz),               Pr-n    1.34(3H, t, J=7.3Hz), 1.49-1.68(3H, m),                               NHEt    1.96-2.08(1H, m), 2.63(1H, septet, J=6.6Hz),                                  3.10-3.19(4H, m), 3.31(2H.dq, J=5.1Hz, J=7.3Hz)                               3.47(1H, dd, J=5.1Hz, J=8.1Hz),                                               3.73(2H, q, J=8.1Hz), 3.88(1H, dt, J=5.1Hz,                                   J=8.1Hz), 6.54(1H, s), 9.69(1H, br)                                           ν.sub.max (neat)(cm.sup.-1):3447, 1590, 1231                       17      δ.sub.TMS (CDCl.sub.3)(ppm):0.92(3H, t, J=7.3Hz),               Pr-n    1.51-1.73(3H, m)                                                      SMe     2.00-2.12(1H, m), 2.44(3H, s),                                                2.66(1H, septet, J=6.6Hz)                                                     3.42-3.60(5H, m), 3.70-3.83(2H, m),                                           3.88(1H, dt, J=5.1Hz, J=8.1Hz), 6.79(1H, s)                                   ν.sub.max (neat)(cm.sup.-1):1542, 1260                             18      δ.sub.TMS (CDCl.sub.3)(ppm):1.47-1.59(1H, m),                   (CH.sub.2).sub.3 -                                                                    1.83(2H, quintet, J=6.6Hz), 1.98-2.11(1H, m),                         OMe     2.59-2.70(1H, m), 2.80(3H, d, J=5.1Hz),                               NHMe    3.01(2H, d, J=6.6Hz), 3.16(1H, dd, J=3.7Hz,                                   J=8.1Hz), 3.31(3H, s), 3.31-3.43(3H, m),                                      3.48(1H, dd, J=5.1Hz, J=8.1Hz), 3.70-3.92(3H, m),                             6.56(1H, s), 9.85(1H, br)                                                     ν.sub.max (neat)(cm.sup.-1):3421, 1637, 1205                       19      δ.sub.TMS (CDCl.sub.3)(ppm):1.53-1.62(1H, m),                   (CH.sub.2).sub.3 -                                                                    1.87(2H, quintet, J=6.6Hz), 1.97-2.11(1H, m),                         OMe     2.44(3H, s), 2.58-2.70(1H, m), 3.32(3H, s),                           SMe     3.39(2H, t, J=6.6Hz), 3.43-3.53(3H, m),                                       3.63(2H, t, J=6.6Hz), 3.70-3.93(3H, m), 6.80(1H, s)                           ν.sub.max (neat)(cm.sup.-1):1542, 1270, 1114                       (Z═N--NO.sub.2,                                                           X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.5 =X.sub.6 =X.sub.7 =H in           formula (1))                                                                  20      δ.sub.TMS (CDCl.sub.3, ppm):1.62-1.74(1H, m),                   H       2.09-2.22(1H, m)                                                      NHMe    2.59-2.79(1H, m), 2.96(3H, d, J=5.1Hz),                                       3.35(2H, t, J=5.1Hz), 3.66-3.80(3H, m),                                       3.92-4.08(1H, m)                                                              ν.sub.max (KBr, cm.sup.-1):3339, 3280, 1618, 1316, 1231, 1169              m.p.:99.5-100.7°C.                                             21      δ.sub.TMS (CDCl.sub.3, ppm):0.95(3H, t, J=7.3),                 H       1.22-1.42(2H, m)                                                      N(Me)Bu-n                                                                             1.58-1.77(3H, m), 2.07-2.18(1H, m), 2.50-2.62(1H, m),                         3.05(3H, s), 3.29-3.46(4H, m), 3.65-3.77(3H, m),                              3.94(1H, dt, J=5.1, J=8.1), 6.51(1H, br.)                                     ν.sub.max (neat, cm.sup.-1):3285, 1626, 1307                       22      δ.sub.TMS (CDCl.sub.3, ppm):1.59-1.72(1H, m),                           2.06-2.18(1H, m)                                                      H       2.56-2.72(1H, m), 3.40(2H, t, J=6.6Hz),                               NHOMe   3.64(1H, dd, J=8.8Hz, J=4.4Hz), 3.70-3.97(3H, m),                             3.88(3H, s), 6.10(1H, br), 10.71(1H, br)                                      ν.sub.max (neat, cm.sup.-1):3293, 1602, 1525, 1433, 1215                   m.p.:95- 106°C.(dec.)                                          23      δ.sub.TMS (CDCl.sub.3, ppm):1.55-1.78(1H, m),                   H       2.06-2.23(1H, m)                                                      N(Me).sub.2                                                                           2.48-2.65(1H, m), 3.10(6H, s), 3.29-3.50(2H, m),                              3.58-3.82(3H, m), 3.85-4.00(1H, m), 6.77(1H, br-s)                            ν.sub.max (KBr, cm.sup.-1):3274, 2940, 1637, 1387, 1075                    m.p.:127.1-128.8°C.                                            24      δ.sub.TMS (CDCl.sub.3, ppm):1.56-1.71(2H, m),                   H       2.01-2.18(2H, m)                                                      N(Me)-  2.48-2.68(2H, m), 3.07(3H, s), 3.20-3.47(3H, m),                      (tetrahy-                                                                             3.60-4.01(9H, m), 6.21-6.83(1H, m)                                    dro-3-  ν.sub.max (neat, cm.sup.-1):3276, 2941, 2869, 1623, 1396,          furanyl)                                                                              1288, 1074, 910                                                       methyl                                                                        25      δ.sub.TMS (CDCl.sub.3, ppm):1.48-1.70(1H, m),                   H       1.94-2.17(1H, m)                                                      N(Me)-  2.41-2.68(1H, m),                                                     benzyl  3.02(3H, s), 3.20-3.97(6H, m), 4.62(2H, s),                                   6.72(1H, br-s), 7.21-7.41(5H, m)                                              ν.sub.max (neat, cm.sup.-1):3283, 1623, 1396, 1297                 26      δ.sub.TMS (DMSO-d.sub.6, ppm):1.47-1.60(1H, m),                 Me      1.85-1.96(1H, m)                                                      NH.sub.2                                                                              2.51-2.62(1H, m), 2.97(3H, s), 3.33-3.51(3H, m),                              3.58-3.71(2H, m), 3.77(1H, dt, J=5.1Hz, J=8.1Hz),                             8.37(2H, br.)                                                                 ν.sub.max (neat, cm.sup.-1):3367, 1623, 1577, 1270                 27      δ.sub.TMS (CDCl.sub.3, ppm):1.50-1.62(1H, m),                   Me      1.95-2.10(1H, m)                                                      NMe.sub.2                                                                             2.56-2.69(1H, m), 2.96(6H, s), 2.99(3H, s),                                   3.26-3.40(2H, m), 3.47(1H, dd, J=5.1, J=8.8),                                 3.70-4.02(3H, m)                                                              ν.sub.max (neat, cm.sup.-1):1439, 1244                             28      δ.sub.TMS (CDCl.sub.3)(ppm):1.20(3H, t, J=7.3Hz),               Et      1.55-1.71(1H, m)                                                      NH.sub.2                                                                              1.97-2.08(1H, m), 2.58-2.70(1H, m),                                           3.32(1H, dd, J=8.1Hz, J=14.7Hz), 3.42-3.50(3H, m),                            3.56(1H, dd, J=5.1Hz, J=8.1Hz), 3.71-3.83(2H, m),                             3.93(1H, dt, J=5.1Hz, J=8.1Hz), 8.24(2H, br)                                  ν.sub.max (neat)(cm.sup.-1):3385, 1616, 1575, 1263                 29      δ.sub.TMS (CDCl.sub.3)(ppm):1.17(3H, t, J=7.3Hz),               Et      1.48-1.72(1H, m)                                                      NHMe    1.95-2.12(1H, m), 2.38-2.52(1H, m),                                           2.98(3H, d, J=5.1Hz)                                                          3.21-3.39(2H, m), 3.52-3.92(6H, m)                                            ν.sub.max (KBr, cm.sup.-1):3299, 1632, 1320, 1235                          m.p.:118.5-125.0°C.                                            30      δ.sub.TMS (CDCl.sub.3, ppm):1.55-1.72(1H, m),                   CH.sub.2 CH═                                                                      1.92-2.09(1H, m)                                                      CH.sub.2                                                                              2.48-2.62(1H, m), 2.78(3H, s),                                        NHMe    3.19(1H, dd, J=8.0, J=13.9)                                                   3.45(1H, dd, J=7.3, J=13.9), 3.49-3.60(1H, m),                                3.70-3.95(5H, m), 5.15-5.27(2H, m), 5.70- 5.89(1H, m),                        8.53(1H, br-s)                                                                .sub.max (KBr, cm.sup.-1):3338, 2935, 1624, 1541                              semi-solid                                                            31      δ.sub.TMS (CDCl.sub.3, ppm):1.38-1.56(1H, m),                   benzyl  1.71-1.96(1H, m)                                                      N(Me)-  2.08-2.33(1H, m), 2.63(3H*1/2, s), 2.65(3H*1/2, s),                   benzyl  2.73-2.82(1H, m), 2.94-3.04(1H, m), 3.30-3.44(1H, m),                         3.64-3.79(3H, m), 4.27(1H, dd, J-15.4, J=3.7),                                4.59(1H, d, J=15.4)                                                           4.91(1H*1/2, d, J=14.7), 4.99(1H, s),                                         5.08(1H*1/2, d, J=14.7), 7.18-7.38(10H, m)                                    ν.sub.max (neat, cm.sup.-1):1656, 1530, 1283, 1079                         m.p.:70-74°C.                                                  32      δ.sub.TMS (CDCl.sub.3, ppm):0.98-1.07(4H, m),                   CO-cyclo-                                                                             1.14-1.23(4H, m)                                                      propyl  1.60-1.75(2H, m), 1.81-1.92(1H, m), 2.01-2.14(1H, m),                 N(Me)CO-                                                                              2.73(1H, br), 3.24(3H, br-s), 3.53-3.58(1H, m),                       cyclo-  3.71-3.94(5H, m)                                                      propyl  ν.sub.max (neat, cm.sup.-1):1698, 1557, 1284                               oily                                                                  33      δ.sub.TMS (CDCl.sub.3, ppm):1.13-1.34(6H, m),                   CO-cyclo-                                                                             1.42-1.92(15H, m)                                                     hexyl   2.00-2.13(1H, m), 2.34-2.48(1H, m),                                   N(Me)CO-                                                                              2.57-2.75(2H, m), 3.19 3H, s), 3.49-3.65(3H, m),                      cyclo-  3.71-3.93(3H, m)                                                      hexyl   ν.sub.max (neat, cm.sup.-1):1704, 1558, 1451, 1287                 34      δ.sub.TMS (CDCl.sub.3, ppm):1.52-1.68(1H, m),                   COCH.sub.3                                                                            2.02-2.14(1H, m)                                                      N(Me)-  2.20(3H, s), 2.40(3H, s), 2.62-2.78(1H, m), 3.16(3H, s)               COCH.sub.3                                                                            3.48-3.95(6H, m)                                                              ν.sub.max (neat, cm.sup.-1):1706, 1558, 1274                               oily                                                                  35      δ.sub.TMS (CDCl.sub.3, ppm):1.11-1.26(6H, m),                   COC.sub.2 H.sub.5                                                                     1.54-1.73(1H, m)                                                      N(Me)-  2.00-2.15(1H, m), 2.33-2.80(5H, m), 3.17(3H, br-s),                   COC.sub.2 H.sub.5                                                                     3.47-3.94(6H, m)                                                              ν.sub.max (neat, cm.sup.-1):1709, 1558, 1461, 1374, 1285           36      δ.sub.TMS (CDCl.sub.3, ppm):1.15-1.26(12H, m),                  COCH-   1.57-1.70(1H, m)                                                      (CH.sub.3).sub.2                                                                      2.02-2.14(1H, m), 2.57-2.76(2H, m),                                   N(Me)-  2.95-3.12(1H, m), 3.22(3H, s), 3.50-3.92(6H, m)                       COCH-   ν.sub.max (neat, cm.sup.-1):1706, 1559, 1286, 1068                 (Me).sub.2                                                                            oily                                                                  37      δ.sub.TMS (CDCl.sub.3, ppm):1.50-1.72(1H, m),                   COCH═                                                                             2.00-2.16(1H, m)                                                      CH.sub.2                                                                              2.57-2.80(1H, m), 3.19(3H, s), 3.53-3.59(1H, m),                      NCO(Me)-                                                                              3.68-3.96(5H, m), 5.80-5.93(2H, m), 6.26-6.63(4H, m)                  CH═CH.sub.2                                                                       ν.sub.max (neat, cm.sup.-1):1698, 1554, 1404, 1284                 38      δ.sub.TMS (CDCl.sub.3, ppm):1.49-1.69(1H, m),                   COOCH.sub.3                                                                           2.07-2.18(1H, m)                                                      N(Me)-  2.60-2.83(1H, br), 3.10-3.36(4H, br),                                 COOCH.sub.3                                                                           3.47-3.62(2H, br)                                                             3.81(3H, s), 3.84(3H, s), 3.71-3.94(3H, m)                                    ν.sub.max (KBr, cm.sup.-1):1690, 1542, 1263, 1057                  39      δ.sub.TMS (CDCl.sub.3, ppm):1.47-1.60(1H, m),                   H       2.04-2.17(1H, m)                                                      N(Me)-  2.44-2.57(1H, m), 3.22-3.28(2H, m), 3.26(3H, s),                      COO-    3.49(1H, dd, J=5.1, J=8.8), 3.78-3.82(2H, m),                         benzyl  3.88(1H, dt, J=5.1, J=8.8), 5.25(2H, s),                                      7.35-7.42(5H, m), 9.71(1H, br.)                                               ν.sub.max (neat, cm.sup.-1):3215, 1733, 1606, 1260, 1163           40      δ.sub.TMS (CDCl.sub.3, ppm):1.50-1.80(1H, m),                   COphenyl                                                                              1.87-2.03(1H, m)                                                      N(Me)CO-                                                                              2.51(3H, s), 2.57-2.70(1H, m), 3.03-3.12(1H, m),                      phenyl  3.19-3.27(1H, m), 3.37-3.54(1H, m), 3.64-3.90(3H, m),                         7.43-7.75(10H, m)                                                             ν.sub.max (KBr, cm.sup.-1):1698, 1545, 1450, 1263                          m.p.: 133-135°C.(dec.)                                         41      δ.sub.TMS (CDCl.sub.3, ppm):1.34(9H, s), 1.35(9H, s),           CO(p-t- 1.54-1.66(1H, m), 1.85-1.96(1H, m), 2.50(3H, s),                      butyl-  2.50-2.62(1H, m), 3.03(1H, dd, J=6.6, J=13.9),                        phenyl) 3.18(1H, dd, J=8.1, J=13.9), 3.35-3.43(1H, m),                        N(Me)CO-                                                                              3.67-3.85(3H, m), 7.46-7.64(8H, m)                                    (p-t-butyl-                                                                           ν.sub.max (KBr, cm.sup.-1):1696, 1542, 1267                        phenyl) m.p.:152.4-153.0°C.                                            42      δ.sub.TMS (CDCl.sub.3, ppm):1.55-1.72(1H, m),                   CO(p-Cl-                                                                              1.88-2.05(1H, m)                                                      Phenyl) 2.53-2.70(1H, m), 2.60(3H, s), 3.13-3.33(2H, m),                      N(Me)CO-                                                                              3.38-3.52(1H, m), 3.66-3.76(2H, m), 3.81-3.89(1H, m),                 (P-Cl-  7.49(2H, d, J=8.1), 7.51(4H, s), 7.62(2H, d, J=8.1)                   phenyl) ν.sub.max (KBr, cm.sup.-1):1692, 1550, 1444, 1267, 1092                    m.p.:149°C.(dec.)                                              43      δ.sub.TMS (CDCl.sub.3, ppm):1.64-1.80(1H, m),                   CO-furyl                                                                              1.93-2.10(1H, m)                                                      N(Me)-  2.66-2.87(1H, m), 3.16(3H, s), 3.51-3.60(1H, m),                      COfuryl 3.71-3.93(5H, m), 6.55-6.60(2H, m), 7.23-7.27(2H, m),                         7.60(2H, d, J=2.2)                                                            ν.sub.max (KBr, cm.sup.-1):1683, 1546, 1473, 1277, 1060            44      δ.sub.TMS (CDCl.sub.3, ppm):1.55-1.67(1H, m),                   COMe    2.00-2.12(1H, m)                                                      NMe.sub.2                                                                             2.16(3H, s), 2.47-2.58(1H, m), 3.13(6H, br.s),                                3.40-3.89(6H, m)                                                              ν.sub.max (KBr, cm.sup.-1):1692, 1590, 1501, 1240                          m.p.:89.0-89.7°C.                                              45      δ.sub.TMS (CDCl.sub.3, ppm):1.19(3H, t, J=7.3),                 COEt    1.54-1.67(1H, m)                                                      NMe.sub.2                                                                             1.97-2.09(1H, m), 2.17-2.58(3H, m), 3.08(3H, br.s),                           3.18(3H, s), 3.43-3.55(2H, m), 3.67-3.90(4H, m)                               ν.sub.max (neat, cm.sup. -1):1685, 1589, 1508, 1247                46      δ.sub.TMS (CDCl.sub.3, ppm):1.64-1.77(1H, m),                   CO-phenyl                                                                             2.00-2.13(1H, m)                                                      NMe.sub.2                                                                             2.55-2.76(7H, m), 3.53-3.62(1H, m), 3.74-3.95(5H, m),                         7.36-7.78(5H, m)                                                              ν.sub.max (neat, cm.sup.-1):1681, 1499, 1255                       47      δ.sub.TMS (CDCl.sub.3, ppm):1,55-1.68(1H, m),                   CON-    2.00-2.18(1H, m)                                                      (CH.sub.3).sub.2                                                                      2.42-2.64(1H, m), 2.81(6H*1/3, s), 3.02(6H*2/3, s),                   NHMe    3.02(6H*1/3, s), 3.19(6H*2/3, s), 3.25-3.32(2H, m),                           3.50-3.57(1H, m), 3.71-3.93(3H, m), 8.99(1H, br)                              ν.sub.max (neat, cm.sup.-1):1683, 1589, 1489, 1385, 1254,                  1124                                                                          oily                                                                  48      δ.sub.TMS (CDCl.sub.3, ppm):1.20-1.34(3H, m),                   Et      1.55-1.70(1H, m)                                                      N(Me)-  2.04-2.17(1H, m), 2.17(3H, s), 2.55-2.85(1H., m),                     COMe    3.11(3H, br.s), 3.25-3.60(4H, m), 3.70-3.95(4H, m)                            ν.sub.max (neat, cm.sup.-1):1695, 1564, 1506, 1256                 (Z═N--CN,                                                                 X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.5 =X.sub.6 =X.sub.7 =H in           formula (1))                                                                  49      δ.sub.TMS (CDCl.sub.3, ppm):1.55-1.66(1H, m),                   H       2.04-2.14(1H, m)                                                      Me      2.34(3H, s), 2.51-2.62(1H, m), 3.36(2H, t, J=6.6Hz),                          3.59(1H, dd, J=5.1Hz, J=8.8Hz), 3.69-3.81(2H, m),                             3.92(1H, dt, J=5.1Hz, J=8.8Hz), 6.04(1H, br.)                                 ν.sub.max (KBr, cm.sup.-1):3260, 2169, 1609, 1561                  50      δ.sub.TMS (CDCl.sub.3, ppm):1.61-1.74(1H, m),                   H       2.06-2.19(1H, m)                                                      SMe     2.50(3H, br.), 2.60(1H, br.), 3.38(2H, br.),                                  3.62-3.81(3H, m), 3.94(1H, dt, J=5.1Hz, J=8.1Hz),                             6.30(1H*1/2, br.), 6.88(1H*1/2, br.)                                          ν.sub.max (KBr, cm.sup.-1):3263, 2165, 1553                                m.p.: 112.8-114.0°C.                                           51      δ.sub.TMS (DMSO-d.sub.6, ppm):1.50-1.60(1H, m),                 Me      1.88-2.00(1H, m)                                                      Me      2.35(3H*3/5, s), 2.36(3H*3/5, s), 2.50-2.62(1H, m),                           2.97(2/5*3H, s), 3.10(3/5*3H, s), 3.35-3.55(3H, m),                           3.58-3.74(3H, m)                                                              ν.sub.max (neat, cm.sup.-1):2175, 1577                             52      δ.sub.TMS (CDCl.sub.3, ppm):0.92(3H, t, J=7.3Hz),               Pr-n    1.54-1.67(3H, m)                                                      NHMe    2.00-2.10(1H, m), 2.54-2.68(1H, m),                                           3.15(3H, d, J=4.4Hz)                                                          3.19-3.40(4H, m), 3.57(1H, dd, J=4.4Hz, J=8.8Hz),                             3.68(1H, dd, J=5.9Hz, J=8.8Hz),                                               3.78(1H, dt, J=5.9Hz, J=8.1Hz),                                               3.93(1H, dt, J=5.9Hz, J=8.1Hz), 5.33(1H, br.)                                 ν.sub. max (neat, cm.sup.-1):3289, 2168, 1553, 1423                (Z═CH--NO.sub.2, X.sub.1 =Me,                                             X.sub.2 =X.sub.3 =X.sub.4 =X.sub.5 =X.sub.6 =X.sub.7 =H in formula (1))       53      δ.sub.TMS (CDCl.sub.3, ppm):1.26-1.33(3H, m),                   H       1.64-1.76(1H, m)                                                      NHMe    2.14-2.30(2H, m), 2.88-2.96(3H, m), 3.20-3.26(2H, m),                         3.71-3.98(3H, m), 6.59(1H, s), 10.23-10.33(1H, m)                             ν.sub.max (KBr, cm.sup.-1):3277, 3212, 3096, 2968, 2872,                   1626,                                                                         1595                                                                          1433, 1375, 1239, 1171, 1139, 1010, 867, 755, 735                             m.p.:127.3°C.-127.9°C.                                  (Z═CH--NO.sub.2, X.sub.5 =Me,                                             X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.6 =X.sub.7 =H in formula (1))       54      δ.sub.TMS (DMSO-d.sub.6, ppm):1.00(3H, d, J=6.6Hz),             H       1.90-2.05(2H, m), 2.65-2.85(3H, br.),                                 NHMe    3.15-3.45(3H, m), 3.75-3.90(3H, m)                                            6.47(1H, br.)                                                                 ν.sub.max (KBr, cm.sup.-1):3274, 1628, 1586, 1367, 1230, 1011              m.p.:127.5-129.0°C.                                            55      δ.sub.TMS (CDCl.sub.3, ppm):1.00-1.10(3H, m),                   Et      1.19(3H, t, J=7.3Hz)                                                  NHMe    1.87-2.07(2H, m), 3.00(3H, d, J=5.1Hz),                                       3.20-4.02(8H, m)                                                              6.54(1H, s), 9.88(1H, br.)                                                    ν.sub.max (neat, cm.sup.-1):3422, 1597, 1236, 1019                 (Z═N--NO.sub.2, X.sub.5 =Me,                                              X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.6 =X.sub.7 =H in formula (1))       56      δ.sub.TMS (CDCl.sub.3, ppm):1.11(3H, d, J=6.6),                 H       2.01-2.14(2H, m)                                                      NHMe    2.96(3H, d, J=5.1), 3.28-3.38(3H, m),                                         3.67(1H, dd, J=4.4, J=8.8),                                                   3.90(1H, dd, J=6.6, J=8.8), 4.07(1H, t, J=6.6)                                ν.sub.max (neat, cm.sup.-1):3304, 1618, 1420, 1233                 (Z═CH--NO.sub.2, X.sub.7 =Me,                                             X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.5 =X.sub.6 =H in formula (1))       57      δ.sub.TMS (CDCl.sub.3, ppm):1.12-1.30(3H, m),                   H       1.63-1.90(1H, m)                                                      NHMe    2.19-2.29(1H, m), 2.64(1H, br.),                                              2.87(3H*1/2, d, J=4.4Hz)                                                      3.00(3H*1/2, d, J=4.4Hz).3.19-3.45(2H, m),                                    3.68-4.13(3H, m), 6.60(1H, s), 10.20-10.25(1H, br.)                           ν.sub.max (KBr, cm.sup.-1):3189, 2968, 1637, 1583, 1541,                   1420,                                                                         1387                                                                          1222, 1171, 999, 750, 700                                                     m.p.:114.0-120.5°C.                                            (Z═N--NO.sub.2, X.sub.7 =Me,                                              X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.5 =X.sub.6 =H in formula (1))       58      δ.sub.TMS (CDCl.sub.3, ppm):1.23(3H*2/3, d, J=6.6),             H       1.31(3H*1/3, d, J=5.9), 1.81-1.90(1H*2/3, m),                         NHMe    2.24-2.34(1H*1/3, m), 2.57-2.71(1H, m),                                       2.96(3H, d, J=5.1), 3.32-3.35(2H, m),                                         3.52-3.57(1H, m), 3.75-3.77(1H, m),                                           3.96-4.02(1H, m), 4.11-4.19(1H, m)                                            ν.sub.max (neat, cm.sup.-1):3305, 2967, 2934, 2869, 1618,                  1561,                                                                         1419                                                                          1328, 1236, 1174, 1145, 787                                           59      δ.sub.TMS (CDCl.sub.3, ppm):1.16-1.28(10H, m),                  COC.sub.2 H.sub.5                                                                     1.76-1.78(1H, m)                                                      NCO(Me)-                                                                              2.26-2.85(5H, m), 3.17(3H, brs), 3.45-4.15(5H, m)                     C.sub.2 H.sub.5                                                                       ν.sub.max (neat, cm.sup.-1):2975, 2944, 2875, 1710, 1559,                  1457,                                                                         1376                                                                          1286, 1208, 1179, 1106, 1059, 953, 887, 834, 816                      (Z═CH--NO.sub.2, X.sub.5 =X.sub.7 =Me,                                    X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.6 =H in formula (1))                60      δ.sub.TMS (CDCl.sub.3, ppm):0.80-1.25(6H, m),                   H       1.97-2.02(1H, m)                                                      NHMe    2.42-2.60(1H, m), 2.87-2.96(3H, m), 3.08-3.51(3H, m)                          3.59-3.76(1H, m), 3.98-4.20(1H, m), 5.85(1H, br-s),                           6.21(1H, br-s), 6.60(1H, s)                                                   ν.sub.max (neat, cm.sup.-1):3262, 3191, 3062, 2968, 2932,                  1637,                                                                         1579                                                                          1421, 1374, 1220, 1170, 997, 749732, 687                                      m.p.:144.4°C.˜145.1°C.                            (Z═N--NO.sub.2, X.sub.5 =X.sub.7 =Me,                                     X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.6 =H in formula (1))                61      δ.sub.TMS (CDCl.sub.3, ppm):0.87-1.30(6H, m),                   H       1.99-2.05(1H, m)                                                      NHMe    2.43-2.54(1H, m), 2.94-2.98(3H, m), 3.21-3.48(3H, m)                          3.63-3.72(1H, m), 3.97-4.14(1H, m)                                            ν.sub.max (neat, cm.sup.-1):3309, 2970, 2934, 2878, 1716,                  1617,                                                                         1569                                                                          1560, 1420, 1328, 1227, 1174, 1145, 1046, 864, 787                    (Z═CH--NO.sub.2, X.sub.6 =X.sub.7 =Me,                                    X.sub.1 = X.sub.2 =X.sub.3 =X.sub.4 =X.sub.5 =H in formula (1))               62      δ.sub.TMS (CDCl.sub.3, ppm):1.22(3H, s), 1.33(3H, s),           H       1.44-1.51(1H, m), 2.02(1H, dd, J=12.5, J'=8.1),                       NHMe    2.69(1H, septet, J=7.3)                                                       2.87(3H*1/2, d, J=4.4), 3.00(3H*1/2, d, J=4.4),                               3.20-3.36(2H, m), 3.56-3.62(1H, m),                                           3.94-4.00(1H, m), 6.32(1H*1/2, br), 6.60(1H, s),                              6.61(1H*1/2, br), 10.25(1H, br)                                               ν.sub.max (KBr, cm.sup.-1):3192, 2967, 1616, 1571, 1387,                   1248,                                                                         1052 988, 926, 764                                                            m.p.:132.0-133.1°C.                                            (Z═N--NO.sub.2, X.sub.6 =X.sub.7 =Me,                                     X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.5 =H in formula (1))                63      δ.sub.TMS (CDCl.sub.3, ppm):1.23(3H, s),                        H       1.34(3H, s), 1.47(1H, dd, J=13.2, J=7.3),                             SMe     2.04(1H, dd, J=13.2, J=8.1), 2.53(3H, s),                                     2.72(1H, septet, J=7.3), 3.36-3.51(2H, m),                                    3.62(1H, dd, J=8.8, J=5.9), 4.00(1H, dd, J=8.8,                               J=6.6), 10.11(1H, br)                                                         ν.sub.max (KBr, cm.sup.-1):3369, 2974, 1562, 1453, 1198,                   1051,                                                                         794                                                                           m.p.:47.1-53.3°C.                                              64      δ.sub.TMS (CDCl.sub.3, ppm):1.22(3H, s), 1.33(3H, s),           H       1.43(1H, dd, J=12.5, J=7.3), 2.01(1H, dd, J=12.5,                     NHMe    J=8.1, 2.68(1H, septet, J=7.3), 2.97(3H, d, J=4.4),                           3.35(1H, t, J=5.1), 3.62(1H, dd, J=8.8, J=5.1),                               3.95(1H, dd, J=8.8, J=7.3)                                                    ν.sub.max (neat, cm.sup.-1):3305, 2970, 1616, 1568, 1418,                  1328,                                                                         1233                                                                          1173, 1047                                                            (Z═N--NO.sub.2, X.sub.5 =Et,                                              X.sub.1 =X.sub.2 =X.sub.3 =X.sub.4 =X.sub.6 =X.sub.7 =H in formula (1))       65      δ.sub.TMS (CDCl.sub.3, ppm):1.07-1.14(3H, m),                   H       1.96-2.20(2H, m)                                                      NHMe    2.45(3H, s), 3.32-3.72(4H, m), 3.94-4.06(2H, m),                              6.58(1H, s), 10.6(1H, br.)                                                    ν.sub.max (neat, cm.sup.-1):3420, 1562, 1341,                      ______________________________________                                                1233                                                              

                                      TABLE 2                                     __________________________________________________________________________    (X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═X.sub.5 ═X.sub.6     ═X.sub.7 ═H in formula (2))                                           Compound No.                                                                  R.sub.11                                                                      R.sub.10  Physical Properties                                                 __________________________________________________________________________    A1        δ.sub.TMS (CDCl.sub.3, ppm): 1.61-1.71(1H, m),                          2.01-2.11(1H, m)                                                    H         2.67-2.72(1H, m), 2.63(3H, s), 3.41-3.60(2H, m), 3.78-3.95          Me        (4H, m), 4.30(2H, s), 4.35(2H, s), 9.62(1H. br-s)                             ν.sub.max (KBr, cm.sup.-1): 3294, 2869, 1596, 1188                         m.p.: 117.5-118.9° C.                                        A2        δ.sub.TMS (CDCl.sub.3, ppm): 1.63-1.71(1H, m),                          2.02-2.12(1H, m), 2.54                                              Me        -2.63(1H, m), 2.67(3H, s), 3.05(3H, s), 3.26-3.93(6H, m)            Me        4.29(2H, s), 4.32(2H, s)                                                      ν.sub.max (neat, cm.sup.-1): 3482, 2940, 2873, 1608, 1375,                 1290                                                                A3        δ.sub.TMS (CDCl.sub.3, ppm): 1.24(3H, t, J=7.3Hz),                      1.58-1.71(1H, m)                                                    Et        1.99-2.19(1H, m), 2.59-2.62(1H, m), 2.67(3H, s), 3.31-3.57          Me        (3H, m), 3.69-3.92(4H, m), 4.36(2H, s), 4.39(2H, s)                           ν.sub.max (neat, cm.sup.-1): 1613, 1325                          A4        δ.sub.TMS (CDCl.sub.3, ppm): 1.54-1.70(1H, m),                          2.01-2.13(1H, m)                                                    CH.sub.2 --CH═CH.sub.2                                                              2.54-2.62(1H, m), 2.64(3H, s), 3.26-3.94(6H, m), 4.01(2H,           Me        d, J=6.6Hz), 4.27(2H, s), 4.34(2H, s), 5.28-5.37(2H, m)                       5.77-5.92(1H, m)                                                              ν.sub.max (neat, cm.sup.-1): 2956, 1594, 1298                    A5        δ.sub.TMS (CDCl.sub.3, ppm): 1.19(3H, t, J=7.3),                        1.57-1.69(1H, m)                                                    Me        1.98-2.10(1H, m), 2.50-2.62(1H, m), 2.86(2H, q, J=7.3)              Et        3.04(3H, s), 3.42(1H, dd, J=7.3, J=13.9), 3.48(1H, dd, J=                     5.1, J=8.8), 3.61(1H, dd, J=7.3, J=13.9), 4.71-4.92(3H, m)                    4.36(2H, s), 4.38(2H, s)                                                      ν.sub.MAX (neat, cm.sup.-1): 1606, 1379, 1273                    A6        δ.sub.TMS (CDCl.sub.3, ppm): 1.19(6H, d, J=6.6),                        1.56-1.67(1H, m)                                                    Me        1.98-2.11(1H, m), 2.53-2.65(1H, m), 3.04(3H, s), 3.18(1H,           Pr-iso    septet, J=6.6), 3.33(1H, J=7.3, J=13.9), 3.49(1H, dd, J=                      5.9, J=8.8), 3.61(1H, dd, J=7.3, J=13.9), 3.71-3.91(3H, m)                    4.43(2H, s), 4.45(2H, s)                                                      ν.sub.MAX (neat, cm.sup.-1): 1609, 1386, 1272                    A7        δ.sub.TMS (CDCl.sub.3, ppm): 1.59-1.69(1H, m),                          1.99-2.10(1H, m)                                                    Me        2.46-2.58(1H, m), 3.03(3H, s), 3.32(1H, dd, J=7.3, J=13.9)          benzyl    3.45(1H, dd, J=8.8, J=5.9), 3.60(1H, dd, J=8.1, J=13.9)                       3.70-3.89(3H, m), 3.98(2H, s), 4.31(2H, s), 4.38(2H, s)                       7.36-7.40(5H, m)                                                              ν.sub.MAX (KBr, cm.sup.-1): 1604, 1388, 1289                               m.p.: 111-114° C.                                            __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    (R.sub.7 ═H in formula (5))                                               Compound No.                                                                  X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5                                   X.sub.6, X.sub.7                                                                         Physical Properties                                                __________________________________________________________________________    B1         δ.sub.TMS (CDCl.sub.3, ppm): 1.36(2H, br.),                             1.52-1.64(1H, m), 1.98-                                            X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    2.10(1H, m), 2.32(1H, septet, J=7.3Hz), 2.72(2H, d, J=             X.sub.5 ═X.sub.6 ═X.sub.7 ═H                                                 7.3Hz), 3.51(1H, dd, J=5.9Hz, J=8.8Hz), 3.75(1H, q, J=                        7.3Hz), 3.82-3.91(2H, m)                                                      ν.sub.MAX (neat, cm.sup.-1): 3363, 1660, 1060                   B2         δ.sub.TMS (CDCl.sub.3, ppm): 1.07(3H, d, J=6.6Hz),                      1.46(2H, br.)                                                      X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    1.78-2.04(2H, m), 2.65(1H, dd, J=8.1Hz, J=12.5Hz), 2.85            X.sub.5 ═Me                                                                          (1H, dd, J=5.1Hz, J=8.1Hz), 3.32(1H, t, J=8.1Hz), 3.57(1H,         X.sub.6 ═X.sub.7 ═H                                                              dd, J=6.6Hz, J=8.1Hz), 3.92-4.03(2H, m)                            B3         δ.sub.TMS (CDCl.sub.3, ppm): 0.92(3H, t, J=7.3),                        1.29-1.42(1H, m)                                                   X.sub. 1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                   1.47-1.56(3H, m), .1.71-1.95(2H, m), 2.66(1H, dd, J=8.8,           X.sub.5 ═Et                                                                          J=12.5), 2.83(1H, dd, J=5.1, J=12.5), 3.41(1H, dd, J=6.6, J=       X.sub.6 ═X.sub.7 ═H                                                              8.8), 3.59(1H, dd, J=5.1, J=8.8), 3.91-4.00(2H, m)                 B4         δ.sub.TMS (CDCl.sub.3, ppm): 1.12(3H, s), 1.21(3H, s),                  1.41(1H, dd,                                                       X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    J=12.5Hz, J=8.8Hz), 1.87-1.95(1H, m), 2.50-2.63(1H, m)             X.sub.5 ═X.sub.6 ═H                                                              2.78(2H, d, J=7.3Hz), 3.48(1H, dd, J=8.8Hz, J=6.6Hz), 3.83         X.sub.7 ═Me                                                                          (1H, dd, J=8.8Hz, J=7.3Hz)                                         Hydrochloric                                                                  acid salt                                                                     __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    (formula (11))                                                                Compound No.                                                                  X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5                                   X.sub.6, X.sub.7                                                              W.sub.3    Physical Properties                                                __________________________________________________________________________    C1         δ.sub.TMS (CDCl.sub.3, ppm): 1.23(3H*1/2, d, J=5.9),                    1.27(3H*1/2, d,                                                    X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    J=5.9), 1.54-1.65(1H, m), 1.78-1.87(1H, m), 2.32(1H, br-s)         X.sub.5 ═X.sub.6 ═H                                                              2.44-2.57(1H, m), 3.51-3.66(2H, m), 3.70-3.87(1H, m), 3.90         X.sub.7 ═Me                                                                          -4.11(2H, m)                                                       W.sub.3 ═OH                                                                          b.p. (4mmHg): 70-74° C.                                     C2         δ.sub.TMS (CDCl.sub.3, ppm): 0.99(3H*1/2, d, J=7.3),                    1.22(3H*1/2, d,                                                    X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    J=7.3)1.84-2.10(3H, m), 3.52-3.63(2H, m), 3.67-3.76(2H,            X.sub.6 ═H                                                                           m), 4.00-4.08(1H, m)                                               X.sub.5 ═X.sub.7 ═Me                                                  W.sub.3 ═OH                                                               C3         δ.sub.TMS (CDCl.sub.3, ppm): 1.22(3H, s), 1.30(3H, s),                  1.43(1H, dd,                                                       X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    J=12.5Hz, J=8.1Hz), 1.90(1H, dd, J=12.5Hz, J=8.1Hz), 2.54-         X.sub.5 ═H                                                                           2.68(1H, m), 2.63(1H, brs), 3.56-3.68(3H, m), 3.97(1H, t,          X.sub.6 ═X.sub.7 ═Me                                                             J=8.1Hz)                                                           W.sub.3 ═OH                                                               D1         δ.sub.TMS (CDCl.sub.3, ppm): 1.24(3H*3/5, d, J=5.9),                    1.28(3H*2/5, d,                                                    X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    J=5.9), 1.61-1.72(1H, m), 1.81-1.90(1H*3/5, m), 2.19-2.27          X.sub.5 ═X.sub.6 ═H                                                              (1H*2/5, m), 2.66-2.79(1H, m), 3.02(3H, s), 3.53(1H*3/5,           X.sub.7 ═Me                                                                          dd, J=9.5, 5.9), 3.78(1H*2/5, dd, J=9.5, 5.9), 4.03-4.25           W.sub.3 ═OSO.sub.2 CH.sub.3                                                          (4H, m).                                                                      ν.sub.MAX (neat, cm.sup.-1): 3355, 2974, 2938, 2873, 1717,                 1457, 1355                                                                    1176, 1092, 1049, 977, 956, 831, 752                               D2         δ.sub.TMS (CDCl.sub.3, ppm): 1.22(3H*3/5, d, J=5.9),                    1.30(3H*2/5, d,                                                    X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    J=5.9), 1.53-1.61(1H, m), 1.82-1.92(1H*3/5, m), 2.08-2.18          X.sub.5 ═X.sub.6 ═H                                                              (1H*2/5, m), 2.72-2.86(1H, m), 3.54(1H*3/5, dd, J=6.6, 8.8)        X.sub.7 ═Me                                                                          3.63-3.84(3H+1H*2/5, m), 3.97-4.04(1H*3/5, m), 4.14-4.21           W.sub.3 ═                                                                            (1H*2/5, m), 7.71-7.90(4H, m)                                      phthalimide                                                                   D3         δ.sub.TMS (CDCl.sub.3, ppm): 0.94-1.26(6H, m),                          1.88-2.00(1H, m)                                                   X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    2.30-2.82(1H, m), 3.41-4.19(5H, m), 7.71-7.89(4H, m)               X.sub.6 ═H                                                                           ν.sub.MAX (neat, cm.sup.-1): 2975, 2937, 2849, 1768, 1709,                 1608, 1467                                                         X.sub.5 ═X.sub.7 ═Me                                                             1438, 1399, 1308, 1089, 1051, 909, 720                             W.sub.3 ═                                                                            m.p.: 71.5° C.˜72.3° C.                        phthalimide                                                                   D4         δ.sub.TMS (CDCl.sub.3, ppm): 1.69-1.81(1H, m),                          1.98-2.11(1H, m)                                                   X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    2.74(1H, septet, J=7.3Hz), 3.61(2H, dd, J=5.9Hz, J=8.1Hz)          X.sub.5 ═X.sub.6 ═X.sub.7 ═H                                                 3.65-3.88(4H, m), 3.95(1H, dt, J=5.9Hz, J=8.1Hz), 7.71-            W.sub.3 ═                                                                            7.80(2H, m), 7.84-7.78(2H, m)                                      phthalimide                                                                              ν.sub.MAX (neat, cm.sup.-1): 1701, 1399, 1050, 719              D5         δ.sub.TMS (CDCl.sub.3, ppm): 1.55(1H, septet, J=6.6Hz),                 1.94-2.07                                                          X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    (1H, m), 2.46(3H, s), 2.59(1H, septet, J=6.6Hz), 3.49(1H,          X.sub.5 ═X.sub.6 ═X.sub.7 ═H                                                 dd, J=5.1Hz, J=9.5Hz), 3.64-3.81(3H, m), 3.92(1H, t, J=            W.sub.3 ═OSO.sub.2 -tolyl                                                            8.8Hz), 3.99(1H, dd, J=6.6Hz, J=9.5Hz), 7.36(2H, d. J=                        8.1Hz), 7.79(2H, d, J=8.1Hz)                                       D6         δ.sub.TMS (CDCl.sub.3, ppm): 1.62-1.76(1H, m),                          2.05-2.16(1H, m)                                                   X.sub.1 ═X.sub.2 ═X.sub.3 ═X.sub.4 ═H                                    2.70(1H, septet, J=7.3Hz), 3.40(2H, dd, J=1.5Hz, J=7.3Hz)          X.sub.5 ═X.sub.6 ═X.sub.7 ═H                                                 3.45-3.53(1H, m), 3.60(1H, dd, J=5.1Hz, J=8.8Hz), 3.80(1H,         W.sub.3 ═Br                                                                          t, J=7.3Hz), 3.89-3.95(1H, m)                                      __________________________________________________________________________

In the same manner as in the preceding Example 1 to 22 and Referenceexample 1 to 7, comparative compound 1 to 3 and 5 which were used inTest example were prepared.

Comparative compound 1

1-{(tetrahydro-2-furanyl)methylamino}-l-methylamino-2-nitroethylene

δ_(TMS) (CDCl₃, ppm): 1.62-1.75 (1H, m), 1.90-2.08 (3H, 2.82 (3H, d,J=5.0Hz), 3.27-3.37 (1H, m), 3.54-3.62 (1H, m), 3.77-3.93 (2H, m),4.02-4.07 (1H, m), 6.58 (1H, s), 6.94 (1H, br), 10.27 (1H, br)

ν_(MAX) (KBr, cm⁻¹): 3265, 3200, 1622, 1584, 1375, 1225, 1010

m.p.: 136°-137.5° C.

Comparative compound 2

1-{(2-furylmethyl)amino}-1-methylamino-2-nitroethylene δ_(TMS) (DMSO-d₆,ppm): 2.67-2.92 (3H, br), 4.30-4.56 (2H, br), 6.36 (1H, d, J=2.9Hz),6.42 (1H, d, J=2.9Hz), 6.45-6.57 (1H, br), 7.63 (1H, br), 9.94 (1H, br),10.19 (1H, br)

ν_(MAX) (KBr, cm⁻¹): 3261, 1629, 1580, 1438, 1382, 1242

m.p.: 135.1°-136.5° C.

Comparative compound 3

1-tetrahydrofurfuryl-2-methyl-3-nitroguanidine

δ_(TMS) (CDCl₃, ppm): 1.54-1.73 (1H, m), 1.87-2.20 (3H, m), 2.94 (3H, d,J=4.5Hz), 3.18-3.35 (1H, m), 3.54-3.71 (1H, m), 3.75-3.95 (2H, m),4.01-4.15 (1H, m), 6.93 (1H, br), 9.41 (1H, br)

ν_(MAX) (neat)(cm⁻¹): 3300, 1640, 1561, 1307, 1205

m.p.: 79.5°-82.5° C.

Next, the insecticidal compositions of the present invention are moreparticularly described by way of the following formulation examples, inwhich all "part or parts" are "part or parts by weight".

Formulation Example 1

20 parts of the compound of the invention, 10 parts of Sorpol 355S(surfactant available from Toho Chem. Co.) and 70 parts of xylene wereuniformly stirred and mixed to give an emulsion.

Formulation Example 2

10 parts of the compound of the invention, 2 parts of sodiumalkylnaphthalenesulfonate, one part of sodium ligninsulfonate, 5 partsof white carbon and 82 parts of diatomaceous earth were uniformlystirred and mixed to give 100 parts of a wettable powder.

Formulation Example 3

0.3 part of the compound of the invention and 0.3 part of white carbonwere uniformly mixed, and 99.2 parts of clay and 0.2 part of Driless A(available from Sankyo Co.) were added thereto and uniformly ground andmixed to give 100 parts of a powder preparation.

Formulation Example 4

2 parts of the compound of the invention, 2 parts of white carbon, 2parts of sodium ligninsulfonate and 94 parts of bentonire were uniformlyground and mixed, and water was added thereto and kneaded, granulatedand dried to give 100 parts of a granular preparation.

Formulation Example 5

20 parts of the compound of the invention and 5 parts of 20% aqueoussolution of polyvinyl alcohol were fully stirred and mixed, and 75 partsof 0.8% aqueous solution of xanthane gum was added thereto and againstirred and mixed to give 100 parts of a flowable preparation.

Formulation Example 6

10 parts of the compound of the invention, 3 parts of carboxymethylcellulose, 2 parts of sodium ligninsulfonate, one part of sodiumdioctylsulfosuccinate and 84 parts of water were uniformly wet-ground togive 100 parts of a flowable preparation.

Next, explanation is made concretely by way of the following testexamples to clarify the excellent insecticidal activity exhibited by thecompounds of the formula (1) according to the invention.

Test Example 1 Effect on Laodelphax striatellus Fallen--smaller brownplanthopper:

The compound of the invention was dissolved in acetone to apredetermined concentration, and 3 ml of the acetone solution wasapplied over a bundle of several rice seedlings (about third leafstage). After drying in air, the treated seedling were covered with ametal gauze cylinder, in which ten female adults of smaller brownplanthopper were released, followed by placing in a temperaturecontrolled room at 25° C. After 48 hours, the mortality was checked. Theresults are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                        Effect on Laodelphax striatellus Fallen -                                     smaller brown planthopper                                                                    Mortality (%)                                                  Test Compound    1000 ppm 200 ppm                                             ______________________________________                                        Nos.       1         100      100                                                        2         100      70                                                         3         100      100                                                        6         100      100                                                        7         100      100                                                        8         100      50                                                        11         100      100                                                       12         100      100                                                       13         100      100                                                       15         100      100                                                       18         100      100                                                       20         100      100                                                       23         100      100                                                       25         100      100                                                       27         100      100                                                       29         100      100                                                       31         100      100                                                       32         100      100                                                       33         100      100                                                       34         100      100                                                       35         100      100                                                       36         100      100                                                       37         100      100                                                       38         100      100                                                       39         100      100                                                       40         100      100                                                       41         100      70                                                        42         100      70                                                        43         100      100                                                       44         100      100                                                       45         100      100                                                       46         100      70                                                        47         100      100                                                       48         100      100                                                       54         100      100                                                       55         100      100                                                       56         100      100                                                       57         100      100                                                       58         100      100                                                       59         100      100                                                       60         100      100                                                       61         100      100                                                       62         100      100                                             Comp. Compound (1)                                                                             0        0                                                   Comp. Compound (2)                                                                             0        0                                                   Comp. Compound (3)                                                                             0        0                                                   Untreated        0        0                                                   ______________________________________                                         Comparative Compound (1):                                                     1{(tetrahydro2-furanyl)-methylamino1-methylamino-2-nitroethylene              Comparative Compound (2):                                                     1{(2furylmethyl)amino1-methylamino-2-nitroethylene                            Comparative Compound (3): 1tetrahydrofurfuryl-2-methyl-3-nitroguanidine  

Test Example 2 Effect on resistant strain of Nepphotettix cincticeptusUnler--resistant green rice leafhopper:

The compound of the invention was dissolved in acetone to apredetermined concentration and 3 ml of the acetone solution was appliedover a bundle of several rice seedlings (about 3rd leaf stage). Afterdrying in air, the treated seedlings were covered with a metal gauzecylinder, in which ten female adults of resistant green rice leafhopperwere released, followed by placing in a temperature controlled room at25° C. After 48 hours, the mortality was checked. The results are shownin Table 6.

                  TABLE 6                                                         ______________________________________                                        Effect on resistant strain of Nephotettix                                     cincticeptus Uhler - resistant green rice                                     leafhopper                                                                                   Mortality (%)                                                  Test Compound    1000 ppm 200 ppm                                             ______________________________________                                        Nos.       1         100      100                                                        2         100      100                                                        3         100      100                                                        4         100      70                                                         5         100      70                                                         6         100      100                                                        7         100      100                                                        8         100      70                                                         9         100      100                                                       11         100      100                                                       12         100      100                                                       13         100      100                                                       14         100      70                                                        15         100      100                                                       16         100      70                                                        18         100      100                                                       20         100      100                                                       21         100      100                                                       23         100      100                                                       24         100      100                                                       25         100      100                                                       26         100      100                                                       28         100      100                                                       29         100      100                                                       30         100      100                                                       31         100      70                                                        32         100      100                                                       33         100      100                                                       34         100      100                                                       35         100      100                                                       36         100      100                                                       37         100      100                                                       38         100      100                                                       39         100      100                                                       40         100      100                                                       41         100      100                                                       42         100      100                                                       43         100      100                                                       44         100      100                                                       45         100      100                                                       46         100      100                                                       47         100      100                                                       48         100      100                                                       49         100      70                                                        50         100      100                                                       51         100      100                                                       52         100      100                                                       53         100      70                                                        54         100      100                                                       55         100      100                                                       56         100      100                                                       57         100      100                                                       58         100      100                                                       59         100      100                                                       60         100      100                                                       61         100      100                                                       62         100      100                                                       63         100      70                                                        64         100      100                                             Comp. Compound (1)                                                                             0        0                                                   Comp. Compound (2)                                                                             0        0                                                   Comp. Compound (3)                                                                             0        0                                                   Untreated        0        0                                                   ______________________________________                                         Comparative Compound (1):                                                     1{(tetrahydro2-furanyl)-methylamino1-methylamino-2-nitroethylene              Comparative Compound (2):                                                     1{(2furylmethyl)amino1-methylamino-2-nitroethylene                            Comparative Compound (3): 1tetrahydrofuryl-2-methyl-3-nitroguanidine     

Test Example 3 Effect on Spodoptera litura Fabricius--Common cutworm

The emulsion of the compound of the invention prepared according toFormulation Example 1 was diluted with distilled water to apredetermined concentration, to which a spreading agent (New Graminavailable from Sankyo Co.) was added at a concentration of 0.02%. Leavesof Ipomea batatas were immersed fully in the dilution. After drying inair, the leaves were transferred into a plastic cup with a diameter of 9cm and a depth of 4 cm. Ten second-instar larvae of Common cutworm wereplace in the cup at 25° C. to eat the leaves. After 72 hours, themortality was checked. The results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                        Effect on Spodoptera litura Fabricus -                                        Common cutworm                                                                               Mortality (%)                                                  Test Compound    1000 ppm 500 ppm                                             ______________________________________                                        Nos.       1         100      100                                                       20         100      100                                                       23         100      100                                                       25         100      80                                                        32         100      60                                                        33         100      80                                                        34         100      80                                                        35         100      100                                                       36         100      80                                                        37         100      70                                                        39         100      80                                                        41         100      60                                                        42         100      100                                                       43         100      80                                                        44         100      60                                                        45         100      60                                                        57         100      80                                                        59         100      60                                              Comp. Compound (1)                                                                             0        0                                                   Comp. Compound (2)                                                                             0        0                                                   Comp. Compound (3)                                                                             0        0                                                   Untreated        0        0                                                   ______________________________________                                         Comparative Compound (1):                                                     1{(tetrahydro2-furanyl)-methylamino1-methylamino-2-nitroethylene              Comparative Compound (2):                                                     1{(2furylmethyl)amino1-methylamino-2-nitroethylene                            Comparative Compound (3): 1tetrahydrofuryl-2-methyl-3-nitroguanidine     

Test Example 4 Effect on Myzus persicae Sulzer--Green peach aphid:

The emulsion of the compound of the invention prepared according toformulation Example 1 was diluted with distilled water to apredetermined concentration, to which a spreading agent (New Graminavailable from Sankyo Co.) was added at a concentration of 0.02%. Thedilution thus prepared was sprayed over eggplant seedlings of 2nd or 3rdleaf stage, on which green peach aphids had been parasitic. Theseedlings were grown in a green house. After 48 hours, the number ofliving aphids was compared to determine the mortality. The results areshown in Table 8.

                  TABLE 8                                                         ______________________________________                                        Effect on Myzus persical Suezer - green                                       peach aphid                                                                                  Mortality (%)                                                  Test Compound    100 ppm  10 ppm                                              ______________________________________                                        Nos.       1         100      50                                                         6         100      100                                                       13         100      56                                                        15         100      51                                                        18         100      45                                                        20         100      100                                                       32         99       40                                                        33         100      72                                                        34         100      60                                                        35         100      77                                                        36         100      73                                                        39         94       34                                                        40         97       41                                                        44         94       72                                                        54         93       0                                                         56         95       33                                                        57         100      61                                                        58         100      65                                                        62         100      77                                                        64         100      96                                              Comp. Compound (1)                                                                             0        0                                                   Comp. Compound (2)                                                                             0        0                                                   Comp. Compound (3)                                                                             0        0                                                   Untreated        0        0                                                   ______________________________________                                         Comparative Compound (1):                                                     1{(tetrahydro2-furanyl)-methylamino1-methylamino-2-nitroethylene              Comparative Compound (2):                                                     1{(2furylmethyl)amino1-methylamino-2-nitroethylene                       

Test Example 5 Effect on Blattella germanica Linne--German cockroach:

The compound of the invention was dissolved in acetone and diluted withacetone to a predetermined concentration. The acetone solution wasapplied on the bottom face of a Tall-skirted dish (height:9 cm,diameter:9 cm). After drying the dish in air, ten male adults of Germancockroach were released therein. After hours, the mortality was checked.The results are shown in Table 9.

                  TABLE 9                                                         ______________________________________                                        Effect on Blatella germanica Linne -                                          german cockroach                                                                             Mortality (%)                                                  Test Compound    1000 ppm 100 ppm                                             ______________________________________                                        Nos.       1         100      100                                                       20         100      100                                                       35         100      100                                                       58         100      100                                             Comp. Compound (4)                                                                             0        0                                                   Untreated        0        0                                                   ______________________________________                                         Comparative Compound (4):                                                     3{(2chloropyridine-5-yl)-methyl1-methyl-2-nitroguanidine (compound            described in Japanese Patent LaidOpen No. 157308/1991)                   

Next, explanation is made concretely by-way of the following testexamples to clarify the insecticidal activity of the intermediates ofthe formula (2) according to the present invention.

Test Example 6 Effect on Laodelphax striatellus Fallen--smaller brownplanthopper:

The compound of the invention was dissolved in acetone to apredetermined concentration and 3 ml of the acetone solution was appliedover a bundle of several rice seedlings (about 3rd leaf stage). Afterdrying in air, the treated seedlings were covered with a metal gauzecylinder, in which ten female adults of smaller brown planthopper werereleased, followed by placing in a temperature controlled room at 25° C.After 48 hours, the mortality was checked. The results are shown inTable 10.

                  TABLE 10                                                        ______________________________________                                        Effect on Laodelphax striatellus Fallen -                                     smaller brown planthopper                                                                      Mortality (%)                                                Test Compound    100 ppm                                                      ______________________________________                                               Nos. A1       30                                                                   A2       100                                                                  A5       100                                                                  A6       100                                                      Comp. Compound (5)                                                                             0                                                            Untreated        0                                                            ______________________________________                                         Comparative Compound (5):                                                     1{(tetrahydro2-furanyl)-methylamino2-nitroimino-5-methylhexahydro-1,3,5-t    iazine                                                                    

Test Example 7 cEffect on resistant strain of Nephotetrix cincticeptusUhler--resistant green rice leafhopper:

The compound of the invention was dissolved in acetone to apredetermined concentration and 3 ml of the acetone solution was appliedon a bundle of several rice seedlings (about 3rd leaf stage). Afterdrying in air, the treated seedlings were covered with a metal gauzecylinder, in which ten female adults of resistant green rice leafhopperwere released, followed by placing in temperature controlled room at 25°C. After 48 hours, the mortality was checked. The results are shown inTable 11.

                  TABLE 11                                                        ______________________________________                                        Effect on resistant strain of Nephotettix                                     cincticeptus Uhler - resistant green                                          rice leafhopper                                                                                Mortality (%)                                                Test Compound    100 ppm                                                      ______________________________________                                               Nos. A1       100                                                                  A2       100                                                                  A5       100                                                                  A6       100                                                                  A7       100                                                      Comp. Compound (5)                                                                             0                                                            Untreated        0                                                            ______________________________________                                         Comparative Compound (5):                                                     1{(tetrahydro2-furanyl)-methylamino2-nitroimino-5-methylhexahydro-1,3,5-t    iazine                                                                    

What is claimed is:
 1. A compound of a formula (2): ##STR12## where X₁,X₂, X₃, X₄, X₅, X₆ and X₇ represent each a hydrogen atom or an alkylgroup having from 1 to 4 carbon atoms; R₁₀ represents an alkyl grouphaving from 1 to 5 carbon atoms or a benzyl group; and R₁₁ represents analkyl group having from 1 to 5 carbon atoms or a benzyl group.
 2. Thecompound of claim 1 wherein X₁, X₂, X₃, X₄, X₅, X₆ and X₇ are each ahydrogen atom.
 3. The compound of claim 2 wherein R₁₀ and R₁₁ are each amethyl group.